CN1028914C - Silver halide color photographic photo sensitive material - Google Patents

Abstract

A silver halide color photographic photosensitive material is disclosed, comprising a support having thereon at least one hydrophilic colloid layer, at least one layer of which is a photosensitive silver halide emulsion layer. At least 50% of the total projected area of the silver halide grains constituting the at least one silver halide emulsion layer is accounted for by tabular grains having an average aspect ratio of at least 2:1, and a yellow colored cyan coupler is contained in at least one hydrophilic colloid layer.

Description

Silver halide color photographic photo sensitive material

The present invention is relevant silver halide color photographic light-sensitive material, more precisely, it is silver halide photographic sensitive material about the high photographic sensitivity that contains plain film shape silver emulsion and new yellow cyan colour coupler, this material has good sharpness, color rendition, graininess, keeping quality and desilverization characteristic.

The colour photographic sensitive material that need have good sharpness and color rendition and high photographic sensitivity now simultaneously, this photosensitive material also can be got express developed.Speech " JP-A " expression " the disclosed Japanese patent application of not examining " that Jap.P. JP-A-61-221748 and JP-A-1-319744(are used here) proposed to improve color rendition, but the sharpness of this photosensitive material and graininess is still improper with yellow cyan colour coupler.

And, use has the plain film shape silver halide particle that the ratio (length breadth ratio) of diameter and thickness was at least 8: 1 and is suggested, for example, in JP-A-58-113934, have good graininess and sharpness as a kind of providing, and the method for the photosensitive material of high photographic sensitivity.

But, when using plain film shape silver halide particle, clearly reduce for the interlayer effect of improving image quality necessity, thereby be unfavorable for color rendition.For overcoming these shortcomings, Jap.P. JP-A-59-129849 and JP-A-61-14635 have proposed to discharge the diffusivity development restrainer and the planar sheet silver halide particle uses jointly, yet, make the improved result of color rendition still can not be satisfactory with these methods.

And when using plane silver halide particle, desilverization characteristic affects adversely, and when adding as United States Patent (USP) 4,552, when disclosed desilverization promoter overcomes these problems in 834, can have a negative impact to Preser Nation of Photographic Materials.

One aspect of the present invention provides has fine details simultaneously, color rendition, graininess and conservatory silver halide colour photographic sensitive material.

The present invention provides the silver halide colour photographic sensitive material that has good desilverization characteristic and can get express developed on the other hand.

Above-mentioned aspect of the present invention is familiar with by such silver halide colour photographic sensitive material is provided, and described photosensitive material contains support, and this support wherein has one deck hydrophilic colloid layer at least; At least one deck sensitive emulsion layer, wherein at least 50% formation at least the total projection area of the silver halide particle of one deck silver halide emulsion layer constitute by having the plain film shape particle that mean aspect ratio was at least 2: 1; And be contained in yellow cyan colour coupler in one deck hydrophilic colloid layer at least.

Yellow cyan colour coupler of the present invention is as described below.

Yellow cyan colour coupler of the present invention is to have absorption maximum at the cyan coupler of 400nm in the 500nm visible-range, and the oxidation state of this colour coupler and aromatic primary amine developer forms absorption maximum and arrives cyan dye between the 750nm visible region at 630nm.

Preferably; the oxidation state coupling of yellow cyan colour coupler of the present invention and aromatic primary amine developer; discharge and contain water-soluble 6-hydroxyl-2-pyridone-5-base azo group; water-soluble pyrazolone-4-base azo group; water-soluble 2-acyl amino phenylazo group, the residual compounds of water-soluble 5-amino-pyrazol-4-base azo group or water-soluble 2-sulfonamido phenylazo group.

The yellow cyan colour coupler of the present invention is represented by formula as described below (C I) to (C IV):

Formula (C I) is in (C IV), and Cp represents cyan coupler residue (T and Cp coupling position bonding); T represents timing group; K represents 0 or 1 integer; X representative by N, O contained among the X or S and (T) _KBonding and the divalent linker that is connected with Q; And Q represents arlydene or divalent heterocyclic group.

In the formula (C I), R ₁And R ₂Independently represent hydrogen atom, carboxyl, sulfo group, cyano group, alkyl, naphthenic base, aryl, heterocyclic radical, carbamyl, sulfamoyl, carboxamide groups, sulfonamido or alkyl sulphonyl separately; And R ₃Represent hydrogen atom, alkyl, naphthenic base, aromatic radical or heterocyclic radical.But, T, X, Q, R ₁, R ₂And R ₃In at least one representative contain the group of water soluble group (for example, hydroxyl, carboxyl, sulfo group, amino, ammonium, phosphono, phosphino-and hydroxyl sulfonyloxy).

In addition, in the formula (C I) Can adopt these tautomeric structure forms as described below, these tautomeric structures are also included within formula of the present invention (C I).

In the formula (C II), R ₄Represent acyl group or sulfonyl; R ₅Represent commutable group, preferably electron donating group is as amino (for example, amino, ethylamino, dimethylamino and lignocaine), alkoxy (for example, methoxyl, ethoxy and propoxyl group) and alkyl (for example methyl, ethyl and isopropyl); And the integer of j representative from 0 to 4.When j represents 2 or when bigger, R ₄Base can be identical or different.But T, X, Q, R ₄And R ₅In at least one contains water soluble group (for example, hydroxyl, carboxyl, sulfo group, phosphono, phosphino-, hydroxyl, sulfonyloxy, amino and ammonium).

In formula (C III) and (C IV), R ₉Represent hydrogen atom, carboxyl, sulfo group, cyano group, alkyl, naphthenic base, aryl, alkoxy, cycloalkyloxy, aryloxy group, heterocyclic radical, carbamyl, sulfamoyl, carboxamide groups, sulfoamido or alkyl sulphonyl; And R ₁₀Represent hydrogen atom, alkyl, naphthenic base, aryl or heterocyclic radical.But, T, X, Q, R ₉And R ₁₀In at least one contains water soluble group (for example, hydroxyl, carboxyl, sulfo group, phosphono, phosphino-, hydroxyl sulfonyloxy, amino and ammonium).And:

Between tautomerism, and represent same compound.

The compound of formula (C I) to (C IV) representative is described in detail below.

Known cyan coupler residue (for example, phenol and aphthols) can be used as the colour coupler residue by the Cp representative.

Preferred Cp example is following formula (Cp-6), (Cp-7) and the colour coupler residue (Cp-8) represented.

In these structural formulas, the free linkage at coupling position place is represented the bonding position of coupling leaving group.

In these structural formulas, work as R ₅₁, R ₅₂, R ₅₃, R ₅₄And R ₅₅When these groups contained diffusion and hinder group, the total number of carbon atoms in them was 8 to 40, and preferably 10 to 30, under other situation, the total number of carbon atoms is no more than 15.Telomerizing with polymer coupler to become under the biform, above-mentioned any substituting group is represented the divalent group with the repetitive binding.In this case, the total number of carbon atoms can exceed above-mentioned scope.

Below, R ₄₁Represent aliphatic group, virtue (family) base or heterocyclic radical; R ₄₂Represent aryl or heterocyclic radical; And R ₄₃, R ₄₄And R ₄₅Represent hydrogen atom, aliphatic group, aryl or heterocyclic radical separately.

R ₅₁, R ₅₂, R ₅₃, R ₅₄, R ₅₅, being described in detail as follows of d and e.

R ₅₁Representative is selected from those R ₄₂The group of representative.R ₅₂Expression is selected from those R ₄₁, Base,

Base,

Base, Base, R ₄₁The O-group, R ₄₁The S-base, halogen atom, or

The group that group is represented.And d represents 0 to 3 integer.When d represents 2 or 3, R ₅₂Group can be identical or different.In addition, R ₅₂Group can be to link mutually to form 4-to 7-member, the divalent group of preferred 5-to 6-member ring texture form, and the divalent group that typically forms ring texture comprises

Draw together

Group.Here, f represents 0 to 4 integer; And g represents 0 to 2 integer.R ₅₃Expression is selected from R ₄₁The group of representative.R ₅₄Expression is selected from R ₄₁The group of representative; And R ₅₅Group is selected from R ₄₁Represented group, R ₄₁The OCONH-group, R ₄₁SO ₂The NH-group,

Group,

Group, R ₄₃The O-group, R ₄₁The S-group, halogen atom (for example, F, Cl, Br) or

Group.When there being a plurality of R ₅₅During group, these groups can be identical or different.

Above-mentioned aliphatic group can be saturated or unsaturation, chain or ring-type, and straight key or side chain replace or unsubstitutedly have 1 to 32 carbon atom, are preferably the aliphatic hydrocarbon group of 1 to 22 carbon atom.Group commonly used comprises methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, isobutyl, tertiary pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl group, 1,1,3,3-tetramethyl butyl, decyl, dodecyl, cetyl and octadecyl.

Aryl preferably has 6 to 20 carbon atoms for replacing or unsubstituted naphthyl or replacement or unsubstituted phenyl.

Heterocyclic radical is preferably 3-to 8-member and replaces or unsubstituted heterocyclic, and this group has 1 to 20 carbon atom, is preferably 1-7 carbon atom, and heteroatoms is selected from nitrogen, oxygen and sulphur atom.Heterocyclic radical commonly used comprises 2-pyridine radicals, 2-thienyl, 2-furyl, 1,3,4-thiadiazoles-2-base, 2,4-dioxo-1,3-imidazolidine-5-base, 1,2,4-triazole-2-base and 1-pyrazolyl.

The above-mentioned substituting group that has in substituent aliphatic group, aryl and the heterocyclic radical comprises halogen atom, R ₄₇O-, R ₄₆S-,

Cyano group and nitro.Here, R ₄₆Represent aliphatic group, aryl or heterocyclic radical; And R ₄₇, R ₄₈And R ₄₉Represent aliphatic group, aryl, heterocyclic radical or hydrogen atom separately.Aliphatic group, the definition of aryl and heterocyclic radical as above.

In the formula (Cp-6), R ₅₁Be preferably aliphatic group or aryl.R ₅₂Be preferably chlorine atom, aliphatic group or R ₄₁CONH-.In addition, d is preferably 1 or 2.R ₅₃Be preferably aryl.

In the formula (Cp-7), R ₅₂Be preferably R ₄₁CONH-.And d is preferably 1.R ₅₄Be preferably aliphatic group or aryl.

In the formula (Cp-8), e is preferably 0 or 1.R ₅₅Be preferably R ₄₁OCONH-, R ₄₁CONH-or R ₄₁SO ₂NH, and these substituting groups preferably are substituted in the 5-position of naphthols ring.

The timing group of being represented by T (timing group) is after the aryl primary amine developer coupling by colour coupler and oxidation state makes the bond rupture that links with Cp, the group that the key that links with X ruptures again.Timing group T is useful on, for example, control coupling reaction activity, stablize colour coupler and control X and with the release timing of other key of X binding.Following radicals can be used as timing group T.Here, * represents the bonding position with Cp, and * * represents the bonding position with X, and perhaps * represents to represent the bonding position with Q with Cp bonding position and * *.

In these structural formulas, R ₁₀Representative can be substituted in the substituting group on the phenyl ring; R ₁₁Expression is selected from R ₄₁Represented group; And R ₁₂Expression hydrogen atom or substituting group.In addition, t represents 0 to 4 integer.R ₁₀And R ₁₂The substituting group of representative comprises R ₄₁-, halogen atom, R ₄₃O-, R ₄₃S-, R ₄₃(R ₄₄) NCO-, R ₄₃OOC-, R ₄₃SO ₂-, R ₄₃(R ₄₄) NSO ₂-, R ₄₃CON(R ₄₃)-, R ₄₁SO ₂N(R ₄₃)-, R ₄₃CO-, R ₄₁COO-, R ₄₁SO-, nitro, R ₄₃(R ₄₄) NCON(R ₄₅)-, cyano group, R ₄₁OCON(R ₄₃)-, R ₄₃OSO ₂-, R ₄₃(R ₄₄) N-, R ₄₃(R ₄₄) NSO ₂N(R ₄₅)-, and

In addition, k represents 0 or 1 integer, and still, usually, k is preferably 0, i.e. direct the and X bonding of Cp.

X representative by N, O or S and (T) _KThe bivalence linking base group of bonding, preferred bivalence linking base group comprise by-O-,-S-,

,-OSO ₂-,-OSO ₂NH-or N and (T) _KThe heterocyclic radical of bonding (for example, from pyrrolidine, piperidines, morpholine, piperazine, the pyrroles, pyrazoles, imidazoles, 1,2, the 4-triazole, benzotriazole, succimide, adjacent dimethyleneimine of benzene oxazolidine-2, the 4-diketone, imidazoline-2, the 4-diketone, 1,2,4-triazolidine-3, the group that the 5-diketone derivatives goes out), and these groups and alkylidene (for example, methylene, ethylidene, propylidene), the ring alkylidene (for example, 1, the 4-cyclohexylene), arlydene (for example, neighbour-phenylene, right-phenylene), divalent heterocycle is (for example, from pyridine, the group that thiophene derives) ,-CO-,-SO ₂-,-COO-,-CONH-,-SO ₂NH-,-SO ₂O-,-NHCO-,-NHSO ₂-,-NHCONH-,-NHSO ₂NH-and-compound binding group between NHCOO-.The most handy formula of X (II) expression:

＊-X ₁-（L-X ₂） _m-＊＊ （Ⅱ）

In the formula (II), * represent with (T) _KBonding position, * * are represented the bonding position with Q; X ₁Representative-O-, or-S-; L represents alkylidene; X ₂Represent singly-bound ,-O-,-S-,-CO-,-SO ₂-,

,

,-SO ₂NH-,-NHSO ₂-,-SO ₂O-,-OSO ₂-,

,-OCNH-,

,-NHSO ₂NH-,

,-OS ₂NH-or-NHSO ₂O-; And m represents 0 to 3 integer.The total number of carbon atoms of X (hereinafter referred to as the C number) is preferably 0 to 12, most preferably is 0 to 8.X is preferably-OCH ₂CH ₂The O-group.

Q represents arlydene or divalent heterocycle.When Q is arlydene; can or (for example have substituting group for condensed ring; halogen atom, hydroxyl, carboxyl, sulfo group, nitro, cyano group, amino, ammonium, phosphono, phosphino-, alkyl, naphthenic base, aryl, carboxamide groups, sulfoamido, alkoxy, aryloxy group, acyl group, sulfonyl, carboxyl, carbamyl and amino-sulfonyl); and the C number is preferably 6 to 15, most preferably is 6 to 10.When Q is divalent heterocycle, heterocyclic radical is for having 3-to 8-member, be preferably 5-to 7-member, monocycle or fused ring heterocycle base, and (for example has a heteroatoms that is selected from N, O, S, P, Se and Te in the ring at least, from pyridine, thiophene, furans, pyrroles, pyrazoles, imidazoles, thiazole, oxazole, benzothiazole benzoxazole, coumarone, benzothiophene, 1,3, the group that 4-thiadiazoles, indoles or quinoline derivatives go out), and can have substituting group (is that substituting group under the arlydene situation is identical with Q), and the C number is preferably 2 to 15, most preferably is 2 to 10.Q is preferably Group.

Thereby, among the present invention-(T) _K-X-Q preferably represents

Work as R ₁, R ₂And R ₃During representation ring alkyl; alkyl can be the straight or branched alkyl; and can contain unsaturated link; and has a substituted radical (for example, halogen atom, hydroxyl, carboxyl, sulfo group phosphono, phosphino-, cyano group, alkoxy, aryl, alkoxy carbonyl group, amino, ammonium, acyl group, carboxamide groups, sulfonamido, carbamyl, sulfonamide and sulfonyl).

Work as R ₁, R ₂Or R ₃During representation ring alkyl, cycloalkanes has 3-to 8-member ring and may be dicyclo.Can contain unsaturated link in the naphthenic base, and can have substituted radical (with R ₁, R ₂Or R ₃Substituting group when representing alkyl is identical).

Work as R ₁, R ₂Or R ₃When representing aryl, aryl can and can have substituted radical (for example, except that working as R for condensed ring ₁, R ₂Or R ₃Outside the substituting group when representing alkyl, add alkyl and naphthenic base).

Work as R ₁, R ₂Or R ₃When representing heterocyclic radical, can be 3-to 8-member (being preferably 5-to 7-member) monocycle or fused ring heterocycle base, and (for example contain a heteroatoms that is selected from N, S, O, P, Se and Te in the ring at least, imidazole radicals, thienyl, pyrazolyl, thiazolyl, pyridine radicals, quinolyl), and can contain substituted radical on the heterocyclic radical (with R ₁, R ₂Or R ₃Substituting group when representing aryl is identical).

Here, carboxyl comprises carboxylate group; Sulfo group comprises sulphonate-base, and phosphino-comprises phosphonium salt base (phosphinate group), and phosphono comprises phosphonate groups, and in this case, and gegenion is, for example, and Li ⁺, Na ⁺, K ⁺Or ammonium ion.

R ₁(for example be preferably hydrogen atom, carboxyl, carbon number and be 1 to 10 alkane, methyl, the tert-butyl group, sulphur methyl, 2-sulfoethyl, ethyloic, 2-carboxyethyl, 2-methylol, benzyl, ethyl, isopropyl), or the aryl with 6 to 12 carbon atoms (for example, phenyl, 4-methoxyphenyl, 4-sulfo group phenyl), and R ₁Be preferably hydrogen atom, methyl or carboxyl.

R ₂Be preferably cyano group, carboxyl; carbamyl with 1 to 10 carbon atom; sulfamoyl group, sulfo group with 0 to 10 carbon atom; alkyl with 1 to 10 carbon atom (for example; methyl, sulphomethyl) have 1 to 10 carbon atom sulfonyl (for example; methyl, sulfonyl, benzenesulfonyl); carboxylic acid amides with 1 to 10 carbon atom (for example; acetylamino, benzamido); or the sulfonamido with 1 to 10 carbon atom (for example; methanesulfonamido, tosyl amino), and R ₂Be preferably cyano group, carbamyl or carboxyl.

R ₃Be preferably hydrogen atom, alkyl (for example methyl, sulphomethyl, ethyloic, 2-thio-ethyl, 2-carboxy ethyl, ethyl, normal-butyl, benzyl, 4-sulfo group benzyl) with 1 to 12 carbon atom, or have aryl (for example, phenyl, 4-carboxyl phenyl), 3-carboxyl phenyl, a 4-methoxyphenyl, 2 of 6 to 15 carbon atoms, 4-dicarboxyl phenyl, 2-sulfo group phenyl, 3-sulfo group phenyl, 4-sulfo group phenyl, 2,4-disulfophenyl, 2, and R the 5-disulfophenyl), ₃Be preferably the alkyl that contains 1 to 7 carbon atom or contain 6 to 10 carbon atom aryl.

R ₄The acyl group of representative formula (III) expression, or the sulfonyl of formula (IV) expression.

R ₁₁SO ₂- （Ⅳ）

Work as R ₁₁When representing alkyl, can be straight key or side chain form, R ₁₁Can contain unsaturated link, and R ₁₁In can contain substituting group (for example, halogen atom, hydroxyl, carboxyl, sulfo group, phosphono, phosphino-, cyano group, alkoxy, aryl, alkoxy carbonyl, amino, ammonium, acyl group, carbon acylamino, sulfonamido, carbamyl, sulfonamide and sulfonyl).

Work as R ₁₁During representation ring alkyl, can be naphthenic base with 3-to 8-member ring, R ₁₁Crosslinked group can be arranged, R ₁₁Can contain unsaturated link, and R ₁₁Can substituted radical (with R ₁₁Substituting group during the expression alkyl is identical).

Work as R ₁₁When representing aryl, can be fused ring aryl, and can contain substituted radical and (for example, remove and R ₁₁Outside substituting group when representing alkyl is identical, add alkyl and naphthenic base).

Work as R ₁₁When representing heterocyclic radical, can be 3-to 8-member's (being preferably 5-person) monocycle or fused ring heterocycle base to 7-member, and have a heteroatoms (for example, imidazole radicals, thienyl, pyrazolyl, thiazolyl, pyridine radicals, quinolyl) that is selected from N, S, O, P, Se and Te at least in the ring, and R ₁₁Can contain substituted radical (with R ₁₁Represent the substituting group of aryl identical).

Here, carboxyl comprises carboxylate groups, and sulfo group comprises sulfonate groups, and phosphino-comprises that phosphonium salt group and phosphono comprise phosphonate groups, and in this case, gegenion is, for example, and Li ⁺, Na ⁺, K ⁺Or ammonium ion.

R ₁₁Be preferably alkyl (for example, methyl, ethyloic, sulfoethyl (Sulfothyl), cyano ethyl) with 1 to 10 carbon, the naphthenic base of 5 to 8 carbon (for example, cyclohexyl, 2-carboxyl cyclohexyl), or the aryl that contains 6 to 10 carbon is (for example, phenyl, 1-naphthyl, 4-sulfo group phenyl), and R ₁₁Be preferably the alkyl that contains 1 to 3 carbon, or contain the aryl of 6 carbon.

R ₅Represent substituted radical, preferably electron donating group is preferably-NR ₆₂R ₆₃Group or-OR ₁₄Base.Preferentially replace in the 4-position.R ₆₂, R ₆₃And R ₁₄Represent hydrogen atom separately, contain the alkyl of 1 to 10 carbon, contain the naphthenic base of 3 to 10 carbon, contain the aryl of 6 to 10 carbon, or heterocyclic radical is as piperidino, morpholino and pyrrole radicals.And, R ₆₂And R ₆₃But between Cheng Huan, and form aliphatic chain rate nitrogen heterocyclic ring more preferably.

In addition, j represents 0 to 4 integer, is preferably 1 or 2, and is preferably 1.

Work as R ₉Or R ₁₀When representing alkyl; can be straight chain or side chain form; described alkyl can contain unsaturated group; and can contain substituted radical (for example, halogen atom, hydroxyl, carboxyl, sulfo group, phosphono, phosphino-, cyano group, alkoxy, aryl, aryloxycarbonyl, amino, ammonium, acyl group, carboxamide groups, sulfonamido, carbamyl, sulfonamide and sulfonyl).

Work as R ₉Or R ₁₀During representation ring alkyl, can be that naphthenic base, the naphthenic base that contains 3-to 8-member ring can have crosslinked group, unsaturated link, and substituted radical can be arranged (with R ₉Or R ₁₀Substituting group when representing alkyl is identical).

Work as R ₉Or R ₁₀When representing aryl, can be fused ring aryl and contain substituting group and (for example, remove and R ₉Or R ₁₀Outside substituting group when representing alkyl is identical, also comprise alkyl and naphthenic base).

Work as R ₉Or R ₁₀When representing heterocyclic radical, can be 3-to 8-member's (being preferably a 5-and 7-member) monocycle or fused ring heterocycle base, and have a heteroatoms (for example, imidazole radicals, thienyl, pyrazolyl, thiazolyl, pyridine radicals, quinolyl) that is selected from N, S, O, P, Se and Te at least in the ring, and R ₉Or R ₁₀Can contain substituted radical (with R ₉Or R ₁₀Substituting group when representing aryl is identical).

Here, carboxyl comprises carboxylate group, and sulfo group comprises sulphonate-base, and phosphino-comprises the phosphonium salt base, and phosphono comprises the phosphonic acids alkali, and in this case, gegenion is for for example, Li ⁺, Na ⁺, K ⁺Or ammonium ion.

R ₉Be preferably cyano group; carboxyl; the amino tetramethyl acyl group that contains 1 to 10 carbon; carbon number is 2 to 10 alkoxy carbon back; carbon number is 7 to 11 aryloxycarbonyl; carbon number is 0 to 10 sulfamoyl; sulfo group; the alkyl of carbon number 1 to 10 (for example; methyl; ethyloic; the sulphur methyl); carbon number be 1 to 10 sulfonyl (for example; mesyl; benzenesulfonyl), carbon number is that 1 to 10 carboxamide groups is (as acetylamino; benzamido), carbon number is 1 to 10 sulfonamido) (as; methanesulfonamido; tosyl amino); alkoxy is (as methoxyl; or aryloxy group (for example, phenoxy group) ethoxy); and most preferably be cyano group; carbamyl; alkoxy carbonyl group, or carboxyl.

R ₁₀Be preferably hydrogen atom, carbon number be 1 to 12 alkyl (for example, methyl, sulphur methyl, ethyloic, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxylic propyl group, 5-sulphur amyl group, 5-carboxylic amyl group, 4-sulphur benzyl) or carbon number be 6 to 15 aryl (for example, phenyl, 4-carboxyl phenyl, 3-carboxyl phenyl, 2,4-dicarboxyl phenyl, 4-sulfo group phenyl, 3-sulfo group phenyl, 2,5-disulfophenyl, 2, and most preferably to be carbon number be that 1 to 7 alkyl or carbon number are 6 to 10 aryl the 4-disulfophenyl),

Cp, X, the Q of formula (C I) to (C IV)

Example described as follows.

The Cp example:

The X example

-O-，-S-，-OCH ₂-，-OCH ₂CH ₂-，

-OCH ₂CH ₂O-，-OCH ₂CH ₂CH ₂O-，

-O（CH ₂CH ₂O） ₂-，-OCH ₂CH ₂S-，

-OCH ₂CH ₂NHCO-，-OCH ₂CH ₂NHSO ₂-，

-OCH ₂CH ₂SO ₂-，-OCH ₂CH ₂OCO-，

-OCH ₂CH ₂CO-，-SCH ₂CONH-，

-SCH ₂COO-，

，

-OCH ₂CH ₂OSO ₂-，-OCO-，

The Q example

The yellow cyan coupler of the present invention who is suitable for is by explanation down, but these examples do not limit described colour coupler scope.

The represented yellow colour former of formula of the present invention (C I) can utilize 6-hydroxyl-2-pyridone usually and contain the aryl diazonium salt or the preparation of the diazo coupling between the heterocycle diazo salt of colour coupler structure.

6-hydroxyl-2-pyridone for example, can use " heterogeneous ring compound-pyridine and derivant thereof " (Heterocyclic Compounds-pyridines and Its Derivatives), the 3rd part, Grinsberg edits (Interscience Publishers, 1962), J.Am.Chem.Soc., 1943, Vol.65, the 449th page, J.Chem.Tech.Biotechnol., 1986, Vol.36, the 410th page, Tetrahedron, 1966, Vol.22, the 455th page, JP-B-61-52827, Deutsches Reichs-Patent 2,162,612,349,709 and 2,902,486, and United States Patent (USP) 3, disclosed method preparation in 763,170.(used here speech " JP-B " expression " authorization Japanese patent specification ").

Diazo salt can utilize, for example, and United States Patent (USP) 4,004,929 and 4,138,258, disclosed method preparation among JP-A-61-72244 and the JP-A-61-273543.Diazo coupling between 6-hydroxyl-2-pyridone and diazo salt can be as methyl alcohol, ethanol, and methyl cellosolve, acetate, N, dinethylformamide, N, N-dimethyl acetyl is pressed, and in tetrahydrofuran ， diox or the hydrosolvent, or carries out in the mixed liquor of these solvents.In this reaction, sodium acetate for example, potassium acetate, sodium carbonate, sal tartari, sodium bicarbonate, NaOH, potassium hydroxide, pyridine, triethylamine, tetramethylurea and tetramethyl guanidine can be used as alkali.Temperature of reaction between-78 ℃ to 60 ℃, is preferably-20 ℃ to 30 ℃ usually.

The synthetic example of yellow colour former of the present invention is by explanation down.

Synthetic example 1

Be used as the preparation of the colour coupler (YC-1) of illustration

NCCH ₂COOCH ₃+H ₂NCH ₂CH ₂SO ₃H→NCCH ₂COOCH ₂CH ₂SO ₃K

The preparation of compound a:

Methyl alcohol (500ml) is added in 125.2g tarine and the 66g potassium hydroxide.With mixture heated and stirring, and in about 1 hour, be added dropwise to the 110g malonic methyl ester nitrile.Mixture heated was refluxed 5 hours, place then and spend the night.The crystal that filtered and recycled is settled out, and with ethanol washing, drying obtains 202.6g compound a crystal at last.

The preparation of compound b:

Water (11.5ml) is added in 11.5g compound a and the 3.5g sal tartari, and the heated and stirred potpourri drips the 7.8g ethyl acetoacetate simultaneously in steam bath.Then potpourri was stirred 7 hours.After the cooling, stir adding 9.2ml concentrated hydrochloric acid, and have crystal settling to come out, the filtered and recycled crystal, and use methanol wash, drying obtains 10.4g compound b crystal subsequently.

Be used as the preparation of the colour coupler (YC-1) of illustration:

To utilize United States Patent (USP) 4,138, the Compound C (10.1g) of disclosed method preparation is dissolved in 60mlN in 258, in dinethylformamide and the 60ml methyl cellosolve, then, and with ice-cooled, adding 4.3ml concentrated hydrochloric acid.Be added dropwise to the solution of forming by 5ml water and 1.84g sodium nitrite then, obtain diazo solution.Then, 60ml methyl cellosolve and 20ml water are added in 7.8g compound b and the 8.2g sodium acetate,, are added dropwise to above-mentioned diazotising solution simultaneously the ice-cooled stirring of potpourri.After dripping, potpourri was stirred 1 hour, then stirring at room 2 hours, and the crystal that is settled out of filtered and recycled.Wash with water and drying, then crystal is dispersed in the 500ml methyl alcohol, reflux 1 hour, cooling then.Filtered and recycled crystal, and use methanol wash, drying obtains the red target compound of 13.6g colour coupler (YC-1) solid of giving an example subsequently.This melting point compound is 269-272 ℃ (decomposition),

And its structure is passed through ¹The HNMR spectrum, mass spectrum and ultimate analysis are determined.In addition, the maximum absorption wavelength of this compound in methyl alcohol is at 457.7nm, and molecular extinction coefficient is 41.300.This compound demonstrates the very big molecular extinction coefficient of spectral absorption preferably as yellow agent.

Synthetic embodiment 2

The preparation of illustration colour coupler (Y-3):

With N, dinethylformamide (75ml) and 75ml methyl cellosolve are added in the 19.2g compound d, compound d is according to disclosed method preparation among the JP-A-62-85242, then, with ice-cooled and stirring, add the 5.6ml concentrated hydrochloric acid, drip the solution that forms by 5ml water and 2.5g sodium nitrite subsequently.After dripping, potpourri was stirred 1 hour, stirring at room 1 hour, obtain diazotising solution then.

Methyl cellosolve (75ml) and 26ml water are added in 10.1g compound b and the 10.7g sodium acetate, with ice-cooled and stir the mixture, simultaneously, prepared diazotising solution above dripping.After dripping, potpourri was stirred 1 hour, then stirring at room 2 hours, the crystal that filtered and recycled is settled out.Then, crystal is dispersed in the 200ml methyl alcohol, is added dropwise to the solution that forms by 10ml water and 2.2g NaOH, and potpourri was stirred 3 hours.Use the concentrated hydrochloric acid neutralise mixt then, with crystal water and the methanol wash that is settled out, dry then.The coarse crystal that obtains according to the method among the synthetic embodiment 1, is purified with hot methanol, obtain 14.8g target compound illustration colour coupler (YC-3).This melting point compound is 246 to 251 ℃ (decomposition), and its structure is passed through ¹The HNMR spectrum, mass spectrum and ultimate analysis are determined.In addition, this compound maximum absorption wavelength in methyl alcohol is 457.6nm, and molecular extinction coefficient is 42,700, and this compound demonstrates good spectral absorption character as yellow colour former.

Synthetic embodiment 3

The preparation of illustration colour coupler (yC-28)

The preparation of Verbindung:

O-amino-acid (137.1g) is added in the 600ml acetonitrile, in the heated and stirred potpourri, in 1 hour, is added dropwise to the 92.5g diketen greatly.After the reflux 1 hour, potpourri is cooled to room temperature, the crystal that filtered and recycled is settled out, and, obtain 200.5g Verbindung crystal with acetonitrile washing and dry.

The preparation of compound f:

With Verbindung (199.1g), 89.2g cyan-acetic ester and 344g28% sodium methoxide are added in 0.9 liter of methyl alcohol, and in autoclave, in 120 ℃ of reactions 8 hours.After placement is spent the night, the concentrating under reduced pressure reaction mixture, add 700ml water and with potpourri with the acidifying of 230ml concentrated hydrochloric acid.The crystal that the collecting precipitation that spends the night goes out, the coarse crystal heated scrub in ethyl acetate and acetonitrile mixed liquor with obtaining obtains 152g compound f.

The preparation of illustration colour coupler (YC-28):

Will be according to United States Patent (USP) 4,138, the compound g(13.0g of 258 disclosed methods preparations) is dissolved in 40mlN, in the dinethylformamide, with ice-cooled and adding 4.5ml concentrated hydrochloric acid, drip the solution that forms by 5ml water and 1.48g sodium nitrite then, obtain diazotising solution.Then, with 20mlN, dinethylformamide and 15ml water are added in 6.0g compound f and the 8g sodium acetate, in stirring and ice-cooled potpourri, add above-mentioned diazotising solution.After dripping, with potpourri stirring at room 30 minutes.Potpourri hcl acidifying, and use ethyl acetate extraction and wash with water, concentrating under reduced pressure then.Concentrate obtains 13g illustration colour coupler (YC-28) yellow crystals with ethyl acetate/methanol mixed solvent recrystallization.The fusing point of this colour coupler (YC-28) is 154 to 156 ℃, and its structure is passed through ¹The HNMR spectrum, mass spectrum and ultimate analysis are determined.In addition, maximum absorption wavelength is at 458.2nm in methyl alcohol for this compound, and molecular extinction coefficient is 42,800, and this compound shows good spectral absorption characteristics as yellow colour former.

The represented yellow colour former of formula (C II) to (C IV) can be according to disclosed method among JP-B-58-6939 and the JP-A-1-197563, and utilizes the method for disclosed colour coupler as preparation formula (C I) representative in the above-mentioned patent to prepare.

Among the present invention, use formula (C I) and C II) the yellow cyan colour coupler of representative is comparatively preferred, and the represented colour coupler of use formula (C I) is best.

Yellow cyan colour coupler of the present invention preferably is added in the photosensitive silver halide emulsion layer or is added to adjacent layer between photosensitive material, and preferably is added in the red sensing coppering silver emulsion layer.Join total amount in the photosensitive material and be 0.005 to 0.30g/m ², be preferably 0.02 to 0.20g/m ², most preferably be 0.03 to 0.15g/m ²

The yellow cyan colour coupler of the present invention can be added to conduct and following identical colour coupler commonly used in the photosensitive material according to identical way.

The detailed description of used tabular silver emulsion as follows among the present invention.

About the used plain film shape silver emulsion of the present invention, mean aspect ratio is represented the mean value of the diameter of silver halide particle for the ratio of thickness.That is, the diameter of every silver halide particle of length breadth ratio representative is divided by the mean value of resulting those values of its thickness (thickness).Here, described diameter is to be construed to microscope or electron microscope observation silver emulsion the time diameter of a circle identical with the particle projection area.Thereby when mean aspect ratio was at least 2: 1, this expression diameter of a circle was the twice of grain thickness at least.

The particle diameter that is used for the plain film shape silver halide particle of silver emulsion of the present invention is at least the twice of grain thickness, and is preferably 3 to 20 times, more preferably 4 to 15 times, preferably is preferably 5 to 10 times.And and the ratio that the sheet silver halide particle accounts for whole silver halide particle projected areas is at least 50%, and preferably is at least 70%, most preferredly is at least 85%.

Use this type emulsion, can obtain having the silver halide photosensitive materials of good articulation.Obtaining of good articulation is owing to observe relatively the very little cause of light scattering of plain film shape emulsion layer with common emulsion layer.By industrial known method, be easy to prove this situation.It is unclear that as for the low reason like this of light scattering degree in plain film shape silver halide emulsion layer, but can be for being because the parallel cause of the orientation of the principal plane of plain film shape silver emulsion and support surface.

In addition, plain film shape silver halide particle diameter of the present invention is 0.2 to 20 μ m, is preferably 0.3 to 10.0 μ m, most preferably is 0.4 to 5.0 μ m.The thickness of particle preferably is no more than 0.5 μ m.Here, plain film shape silver halide particle diameter is the diameter of a circle identical with the particle projection area.And, the distance expression between two parallel surfaces that grain thickness is made of plain film shape silver halide particle.

Among the present invention, the particle diameter of preferred plain film shape silver halide particle is at least 0.3 μ m and super this 10.0 μ m, and grain thickness is no more than 0.3 μ m, and in addition, average (diameter/thickness) value is at least 5 but be no more than 10.If surpass these values, when photosensitive material is folded, when closely twining or touching sharp keen material, photosensitive property takes place unusual, and this does not wish to take place.Contains particle diameter and be at least 0.4 μ m and be no more than 5.0 μ m, and average (diameter/thickness) value is at least 5, and plain film shape silver halide to account for the silver halide magenta-sensitive emulsion of total projection area at least 85% of whole silver halide particles the most preferred.

The used plain film shape silver halide particle of the present invention is by silver chloride, silver bromide, chlorine silver bromide emulsion, iodine silver bromide emulsion or chlorine iodine silver bromide emulsion are formed, but silver bromide preferably, content is no more than the chlorine iodine silver bromide that the iodine silver bromide of 15mol% silver iodide or chlorine silver bromide or content are no more than 50mol% silver chloride and 2mol% silver iodide, and in the silver halide that mixes, the distribution of component can be evenly or the location.

And particle size distribution can be random.

The used plain film shape silver emulsion of the present invention is edited the 66th to 72 page of " photosensitive emulsion chemistry " (the photographic Emulsion Chemistry) of (Focal press, New York, 1966) at Duffin; In the report of Cugnac and Chateau and the phot.Journal of A.P.H.Trivelli and W.D.Smith, 80, (1940), open in the 285th page, and with reference to JP-A-58-113927, disclosed method among JP-A-58-113928 and the JP-A-58-127921 can be easy to make plain film shape silver emulsion.

For example, by than higher pAg value the time, pBr is no more than under 1.3 the condition, and the plain film grain amount that exists is at least under 40% situation and forms crystal seed, under the similar pBr value of maintenance, the hydroponics crystal seed that adds silver and halogen simultaneously obtains plain film shape silver emulsion.Soluble silver salt and halide solution preferably add in the mode that does not have new nucleus to generate in the particle growth process.

The big I of plain film shape silver halide particle is by the control temperature, and used silver salt and halid adding speed is controlled in selection solution type and character and the control particle growth process.

In preparation plain film shape halogen silver of the present invention particle process, by using used ag halide solvent, may command grain size, coating of particles (for example, the diameter/thickness ratio), the growth rate of particle size distribution and particle.Used quantity of solvent is preferably 10 ^-3To 1.0wt% reaction solution scope, most preferably be 10 ^-2To 10 ^-1In the wt% reaction solution scope.Among the present invention, along with used quantity of solvent increases, growth rate also increases, and particle size distribution trends towards single diffusion.On the other hand, along with used quantity of solvent increases, the thickness of particle also tends to thicken.

Known ag halide solvent can be with in the present invention.Usually used ag halide solvent comprises, for example, and ammonia, thioether, thiocarbamide, thiocyanates and thiazoline thioketones.Can reference, for example, United States Patent (USP) 3,271,157; The thioether solvent of being correlated with in 3,574,628 and 3,790,387.In addition, can be with reference to relevant thiocarbamide among JP-A-53-82408 and the JP-A-55-77737, United States Patent (USP) 2,222,264; The thiazoline thioketones solvent of being correlated with among thiocyanates of being correlated with in 2,448,534 and 3,320,069 and the JP-A-53-144319.

As United States Patent (USP) 3,890,154; 3,901,711,4,173,483,4,269,927 and 4,835,093 and European patent 264288 described in, in the generative process and physical ripening process of silver halide particle, allow to exist, for example, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt and complex salt thereof, rhodium salt and complex salt thereof, and molysite and complex salt thereof.

When the used plain film shape silver halide particle of preparation the present invention, preferentially make silver salt solution (for example, water-soluble AgNO ₃And halide solution () adding speed for example, water-soluble KBr solution, addition and add concentration and increase solution), to accelerate the method that particle generates.For example, with reference to United States Patent (USP) 1,335,925; 3,650,757,3,672,900 and 4,242,445, among JP-A-55-142329 and the JP-A-55-158124 with these method relevant portions.

Can comprise multiple compound in the used photosensitive emulsion among the present invention, can be used for preventing in preparation, store or the photographic process of photosensitive material in photographic fog or sense of stability optical property take place.That is to say, the multiple compound of known antifoggant and stabilizing agent, for example, azole such as benzothiazolium salt, nitroimidazole, triazole, benzotriazole, benzimidazole (the especially benzimidazole of nitro or halogen replacement); Heterocyclic mercapto compound, as thyroidan, mercaptobenzothiazoler, mercaptobenzimidazole, dimercaptothiodiazole (mercaptothiadiazoles), mercapto-tetrazole (especially 1-phenyl-5-mercapto-tetrazole), mercaptopyrimidine; Above-mentioned heterocyclic mercapto compound can contain water soluble group, for example, and carboxyl or sulfo group; Thione compounds, Li such as oxazoline thioketones; The azepine indenes, for example, benzotriazole, the purine (especially (1,3,3a, the 7)-purine of 4-hydroxyl-replacement); Benzene thiosulfonic acid and benzenesulfinic acid can be added in the photosensitive emulsion, with reference to United States Patent (USP), and 3,954,474,3,982,947; 4,021,248 or JP-B-52-28660, can obtain the detailed content of embodiment and the using method of these materials.

Above-mentioned emulsion of the present invention preferably singly spreads emulsion.

Single diffusion emulsion of the present invention is to have the emulsion that the coefficient of variation S/ r long-pending relevant with the grain of silver halide particle is no more than 0.25 particle size distribution.Here, r represents average particle long-pending, and S represents standard error.Like this, if each independent grain size is ri, and the silver halide particle number is ni, and the long-pending r of average particle is defined by following formula:

r＝ (∑ni·ri)/(∑ni)

In addition, standard error S is defined by following formula:

The size of single particle represents to utilize this professional known method among the present invention, as T.H.James at The Theory of the photographic process, the third edition, the method described in the 36th to 43 page are equivalent to the diameter of projected area when silver emulsion is carried out cinephotomicrography (being generally the electron microscope photography).Here, the homolographic projection area of silver halide particle is defined as diameter of a circle, this area equals the silver halide particle projected area described in the above-mentioned list of references.Therefore, long-pending r of above-mentioned average particle and standard error S thereof can obtain under (for example, when particle is a cube, octahedron, the tetrakaidecahedron, plain film shape or potato shape) situation except that sphere in the shape of silver halide particle.

The variation factor of silver halide particle size can not surpass 0.25, and preferably is no more than 0.20, preferably preferably is no more than 0.15.

Disclosed single diffusion hexahedron plain film shape silver halide particle is particularly suited for as sheet silver emulsion of the present invention among the JP-A-63-151618.

Here, { 1,1,1 } flat shape of hexahedron plain film shape silver halide particle is a hexagon, and has the adjacent side ratio and be no more than 2 character.Here, the adjacent side ratio represents to form the ratio of hexagonal longest edge length to bond length.If less than 2, then the angle is considered to circular in abutting connection with ratio.At the angle is under the circular situation, and the length of side is extended distance expression between the point of crossing by extended line of adjacent side direct part and the limit straight line portion considered.The hexagonal side length of hexahedron plain film shape particle of the present invention is preferably 1/2 of its basic straight length at least, most preferably is 4/5 of its basic straight length at least.Among the present invention, preferred adjacent side ratio is 1 to 1.5.

Hexahedron plain film shape silver emulsion of the present invention is made up of dispersive medium and silver halide particle, and at least 50%, is preferably to 70%, and the total projection area that most preferably is at least 90% silver halide particle is made of above-mentioned hexahedron plain film shape silver halide particle.

Among the present invention, the halide component of hexahedron plain film shape silver halide particle can be a silver bromide, the iodine silver bromide, and chlorine silver bromide or chlorine iodine silver bromide, but be preferably silver bromide or iodine silver bromide.In the iodine silver bromide, agi content is that preferred 2 to 15mol% greater than 0 to 30mol%, and most preferably 4 to 12mol%.Silver iodide is distributed in the whole particle to uniformly in the particle, perhaps in granule interior and top layer, agi content can be different, and perhaps particle has the sandwich construction of different agi content layers, and the agi content on preferred particulates surface is less than the interior iodine type particle of granule interior.

With reference to United States Patent (USP) 4,797, the relevant method for preparing hexahedron plain film shape silver emulsion in 354.

The preparation of single diffusion hexahedron silver emulsion can be divided into nucleus and form, physical ripening (Ostwald ripending) and particle growth step, form in the journey at nucleus, the pBr value maintains 1.0 to 2.5, and nucleus is formed on supersaturated condition (temperature, gelatin concentration, water-soluble silver salt solution and water-soluble alkali belong to the adding speed of halide solution, the pBr value, iodide ion content, stirring rate, the pH value, the concentration of ag halide solvent content and salt, or the like) under carry out form so that obtain having the optimized nucleus of parallel twin crystalline substance (body flat) face (plain film shape particle nucleus).In the physical ripening process, regulate temperature, the pBr value, the pH value, gelatin concentration and ag halide solvent amount, etc., make the particle that generates in the nucleating process, rather than plain film shape particle, dissolving.Like this, plain film shape nucleus growth is in fact only arranged, thereby obtain having the diffusible nucleus of good list.Then, by the silver ion that adds in control pBr value and the particle growth process and the amount of halogen ion, a length breadth ratio and a hexahedron plain film shape silver halide particle that amasss that can obtain having regulation.The adding speed of silver ion and halogen ion is preferably 30% to 100% of limit rate of crystal growth in the particle developmental process.

Plain film shape silver emulsion of the present invention will carry out the chemical sensitization effect usually.

The silver emulsion formation that chemical sensitization acts on is as previously described carried out afterwards, and above-mentioned emulsion can wash with water before the chemical sensitization effect after silver emulsion forms.

Chemical sensitization acts on Research Disclosure, NO.17643(1978 Dec, the 23rd page) and Research Disclosure, NO.18716(1979 November, the 648th page of right hurdle) existing narration in, and can be 5 to 10 at PAg, pH is 5 to 8, temperature is under 30 ℃ to 80 ℃, utilize sulphur, selenium, tellurium, gold, platinum, palladium, the combination of iridium or these sensitizers is carried out.

And in the presence of spectral sensitizing dye, plain film shape silver emulsion of the present invention preferably carries out chemical sensitization.Chemical sensitization action method in the presence of spectral sensitizing dye has been disclosed, for example, at United States Patent (USP), 4,425,426 and 4,442,201, JP-A-59-9658 is among JP-A-61-103149 and the JP-A-61-133941.Usually the spectral sensitizing dye that is used in the silver halide photosensitive materials can be used for this purpose, and useful spectral sensitizing dye is at Research Disclosure, No.17643, the the 23rd and 24 page and Research Disclosure, No, 18716,649 pages of right hurdles, the 648th page of right hurdle to the in open.

Can use the spectral sensitizing dye of single type, perhaps use the composition of this dyestuff.

The joining day of spectral sensitizing dye can be before the chemical sensitization effect begins (in the particle forming process, after particle forms and finishes or after the water washing), in the chemical sensitization mechanism, or after the chemical sensitization effect finishes.Particle form finish after and the chemical sensitization effect begin before or after the chemical sensitization effect was finished, the adding spectral sensitizing dye was comparatively preferred.

The addition of spectral sensitizing dye depends on specific purposes, but uses 30 to 100% saturated absorption amount usually, and 50% to 90% saturated absorption amount preferably.

Plain film shape silver emulsion of the present invention need carry out the spectral sensitization effect usually.Spectral sensitizing dye among above-mentioned spectral sensitizing dye and the above-mentioned two pieces of Research Disclosures can be used as spectral sensitizing dye.As mentioned above, make the emulsion that contains spectral sensitizing dye that the time spent prepares, utilize identical dyestuff or dissimilar dyestuff can further carry out the spectral sensitization effect continuously in chemical sensitization.

Plain film shape emulsion of the present invention can be used for sensitive emulsion layer separately, maybe will have two or more long-pending emulsions of different average particle and maybe will have two or more emulsions mixing of different agi contents and be used for same photographic layer.The viewpoint that the use of aforesaid mixed emulsion is preferentially controlled from contrast, wide exposure range graininess control, and color developer correlativity control (for example, the correlativity of colored developer component in time and the sodium sulfite salt developer solution, and the correlativity of pH) is considered.

In addition, the used emulsion of the present invention discloses in JP-A-60-143332 and JP-A-60-254032, and the relative standard deviation of agi content preferably is no more than 20% between particle.

Among the present invention, use the compound of following formula (A) expression to improve photographic sensitivity, graininess and desilverization characteristic are the most reasonable.

Q-SM ¹（A）

In the following formula, Q represents and is selected from least-SO ₃M ²,-COOM ²,-OH and-NR ¹R ²In a group direct-type indirectly by the heterocyclic group as the divalent group bonding of alkylidene, M ¹And M ²Independently represent hydrogen atom, alkaline metal, quaternary ammonium ion or quaternary phosphonium ion, and R separately ¹And R ²(can be identical or different) represents hydrogen atom or replacement or unsubstituted separately, and carbon number is 1 to 6 alkyl (for example, methyl, ethyl, isopropyl).

The example of the heterocyclic group practicality of Q representative comprises: oxazole ring, thiophene miaow ring, imidazole ring, selenazoles ring in the formula (A), triazole ring, tetrazole ring, thiadiazoles ring oxadiazole ring, pentazole ring, pyrimidine ring, the thiazine ring, triazine ring and thiadiazine ring, and and the ring of other carbocyclic ring or heterocycle bonding, for example, the benzothiazole ring, benzotriazole ring, benzimidazole ring benzoxazole ring, benzo shines azoles ring, Nai Bing oxazole ring, three azepine pyrrolo-es [1,2-α] pyridine ring, diaza pyrrolo-[1,2-α] pyridine ring and four azepine pyrrolo-es [1,2-α] pyridine ring.

The formula (B) and the compound (C) represented of sulfhydryl heterocycle compound that is selected from formula (A) representative is especially suitable

In formula (B), Y and Z represent nitrogen-atoms or CR independently of one another ⁴(R wherein ⁴Represent hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl), R ³Representative is by at least one organic residue that is selected from the substituting group replacement of following radicals, and they are-SO ₃M ²,-COOM ²,-OH and-NR ¹R ², practical R ³Example comprise: the alkyl of 1-20 carbon atom (as, methyl, ethyl, propyl group, hexyl, dodecyl, octadecyl) and the aryl of 6-20 carbon atom (as, phenyl, naphthyl), L ¹It is selected from representative-linking group ,-S-, and-O-,

,-CO-,-SO-and-SO ₂-, n is 0 or 1.

Above-mentioned alkyl of mentioning and aryl can be replaced by other substituting group, as halogen atom (as, F, Cl, Br), alkoxy (as, methoxyl, methoxy ethoxy), aryloxy group (as, phenoxy group), alkyl (R wherein ²Be aryl), aryl (is worked as R ²During for alkyl), acylamino-(as, acetylamino; benzamido), carbamyl (as, unsubstituted carbamyl; the phenyl amino formoxyl, the methylamino formoxyl), sulfonamido (as; sulfonyloxy methyl amino, the phenyl sulfonamido), amino-sulfonyl (as; unsubstituted amino-sulfonyl, methylamino sulfonyl, phenyl amino sulfonyl); sulfonyl (as, methyl sulphonyl, phenyl sulfonyl); sulfinyl (as; the methyl sulfenyl, the phenyl sulfenyl), cyano group; alkoxy carbonyl (as; methoxycarbonyl), aryloxycarbonyl (as, phenyloxycarbonyl) and nitro.

As two or more substituted radical-SO ₃M ,-COOM ²,-OH and-NR ¹R ²And R ³The time, these substituting groups can be identical or inequality.

R ¹, R ², M ¹And M ²And the same meaning in the formula (A).

In formula (C), X represents sulphur atom, oxygen atom or

, R ⁵Represent hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl, they are selected from R in the formula (B) ⁴The group of representative.

L ²Representative-CONR ⁶-,-NR ⁶CO-,-SO ₂NR ⁶-, NR ⁶SO ₂-,-OCO ,-COO-,-S-,-NR ⁶-,-CO-,-SO-,-OCOO-,-NR ⁶CONR ⁷-,-NR ⁶COO-,-OCONR ⁶-or-NR ⁶SO ₂NR ⁷-,

R ⁶And R ⁷Represent hydrogen atom separately, be selected from R in the formula (B) ⁴The replacement of representative or not substituted alkyl or replacement or unsubstituting aromatic yl.

R ³Or M ¹With formula (A) with the same meaning (B), n represents 0 or 1.

In addition, R ⁵, R ⁶And R ⁷The substituted alkyl of representative and the substituted radical and the R of substituted aryl ⁴The content of the substituted radical of representative is identical.

In above-mentioned formula, R ³Optimumly be-SO ₃M ²Or-COOM ²

The example that is applicable to the preferred compound of formula of the present invention (A) representative is described as follows:

The compound of formula A representative is known, and the available following list of references and the method for patent disclosure make.

U.S.Parents 2,585,388 and 2,541,924, JP-B-42-21842, JP-A-53-50169, BrP 1,275,701, D.A.Berfes etc., Journal of Heterocyclic Chemistry, Vol.15, No.981(1978), The Chemistry of Heterocyclic Chemistry, Imidazole and Derivatives, the part I, the 336-339 page or leaf, Chemical Abstracts, 58, No.7921(1963), 394 pages, E.Hoggarth, Journal of the Chemical Society, 1160-1167 page or leaf (1949) and S.R.Sandler and W.Karo, Organic Functional Group Preparations, Academic Press, 312-315 page or leaf (1968), M.Chamdon et al., Bulletin de la Societe Chemique de France, 723(1954), D.A.Shirley and D.W.Alley, J.Am.Chem.Soc., 79,4922(1954), A.Whol and W.Marchwald, Berichte(German Chemical Society Journal), Vol.22,568 pages (1889), J.Am.Chem.Soc., 44, the 1502-1510 page or leaf, U.S.Patent 3,017,270, British Patent 940,169, JP-B-49-8334, JP-A-55-59463, Advances in Heterocyclic Chemistry, 9,165-209(1968), West German Patent 2,716,707, The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives, Vol.1,384 pages, Organic Syntheses IV, 569(1963), Berichte, 9,465(1976), J.Am.Chem.Soc., 45,2390(1923), JP-A-50-89034, JP-A-53-28426, Jp-A-55-21007 and JP-A-40-28496.

The compound of formula A representative be contained in silver halide emulsion layer or other hydrophilic colloid layer (as, middle layer, sealer, Yellow filter layer, antihalation layer), but it preferably be contained in silver halide emulsion layer or the layer that adjoins with it in.

In addition, the added amount of compound of formula (A) representative adds 1 * 10 from every square metre of photosensitive material ^-7To 1 * 10 ^-3Mol/m ², preferably 5 * 10 ^-7-1 * 10 ^-4Mol/m ², most preferably 1 * 10 ^-6-3 * 10 ^-5Mol/m ²

Photosensitive material of the present invention can be included on the support, the blue silver halide emulsion layer of at least a sense, silver halide emulsion layer that at least a sense is green and the red silver halide emulsion layer of at least a sense, but the quantity and the order of silver halide emulsion layer and non-photographic layer do not had special mandatory restriction.Typically, silver halide photographic sensitive material contains the photosensitive material layer that one deck is made up of a plurality of silver halide emulsion layers at least on support, emulsion layer has same colour sensitivity basically, but different light sensitivity is arranged, and described photosensitive layer is the unit photosensitive layer to blue light, green glow or ruddiness sense look.In the multilayer color silver halide photographic-material, the arrangement of unit photosensitive layer usually is, from support one side is in order, feels red elementary layer, feels green elementary layer, the blue elementary layer of sense.Yet as need, this order is reversible, each layer can be arranged to: interlayer with same colour sensitivity clips different colour sensitivity.

Various non-photosensitivity layers as the middle layer, can be placed in the centre of above-mentioned silver halide photosensitive layer, and as the highest and lowermost layer.

Colour coupler and DIR compound can be contained in the middle layer, as are disclosed in JP-A-61-43748, JP-A-59-113438, J-A-59-113440, those of JP-A-61-20037 and JP-A-61-20038 also can contain anti-blending agent in middle layer, as normally used those.

The a plurality of silver halide emulsion layers that constitute each unit photosensitive layer are double-decker preferably, comprises a high sense emulsion layer and a low sense emulsion layer, as in Deutsches Reichs-Patent 1,121,470 or BrP 923,045 in disclosed like that.Usually, preferably in layer, settle layer, can between each silver halide emulsion layer, use non-photographic layer than low speed near support.In addition, low sense layer can be arranged in the one side away from support, and high sense layer then is positioned near the one side of support, and for example they are disclosed in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.

In actual use, from from support one side farthest, can be arranged to, the blue layer of low speed sense (BL)/the blue layer of sense (BH)/high speed green layer (GH)/low speed green layer (GL)/high speed felt red beds (RH)/low speed sense red beds (RL) at a high speed, or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH.

In addition, away from the one side of support, each level preface can be arranged (being disclosed in JP-B-55-34932) like this from: the blue layer/GH/RH/GL/RL of sense.Further, away from the one side of support, each layer can be as being disclosed in the order of JP-A-56-25738 and JP-A-62-63936: the blue layer/GL/RL/GH/RH of sense from.

Moreover, as disclosed among the JP-B-49-15495, effectively arrange and comprise that those have three layers of layer with different film speeds therein, make the lower layer of light sensitivity with respect to support, the silver halide emulsion layer that makes top high photographic sensitivity is at the top, make silver halide emulsion layer do the middle layer, and make the silver halide emulsion layer of the light sensitivity lower make bottom than the middle layer with light sensitivity lower than above-mentioned top layer.Under the situation of this three-decker with the light sensitivity that has nothing in common with each other, disclosed as the JP-A-59-202464 instructions, each layer that has in the elementary layer of identical colour sensitivity can be by following sequencing, from away from the one side of support; Middling speed emulsion layer/high-speed emulsion layer/low speed emulsion layer.

In addition, each layer can following sequencing, for example high-speed emulsion layer/low speed emulsion layer/middling speed emulsion layer, or low speed emulsion layer/middling speed emulsion layer/high-speed emulsion layer.

Further, have four layers/or during multilayer, the arrangement of carrying out with aforesaid way can also change.

As above-mentioned, can select various layer structure and arrangement, this correspondingly will depend on the final use of photosensitive material.

Except above-mentioned dull and stereotyped emulsion used, the silver emulsion that the present invention uses was described as follows:

In the sensitive emulsion layer of photographic light-sensitive material of the present invention, the silver halide of preferred combination is to contain iodine silver bromide, the silver iodochloride that is no more than the 30mol% silver iodide, or iodine chlorine silver bromide.Optimum silver halide is to contain iodine silver bromide or the iodine chlorine silver bromide of about 2mol% to about 10mol% silver iodide.

Silver halide particle in the photosensitive emulsion can be a rule crystallization form such as cuboidal, octahedron or tetrakaidecahedron form, and irregular crystal form such as ball or tabular form have the form such as the twin plane of crystal defect or the complex form of these forms.

Silver halide can be the meticulous silver halide particle of particle size less than about 0.2 μ m, or the larger particles of the about at the most 10 μ m of projecting plane diameter, but emulsion polydispersion emulsion or single emulsion that disperses.

Being used for silver halide magenta-sensitive emulsion of the present invention can be with preparing as following document disclosed method, as Research Disclosure(RD), NO.17643(1978,12), P22 and P23 " I.Emulsion Preparation and Types ", Research Disclosure, NO.18716(11,1979), P648 and Research Disclosure, NO.307105(11.1989), P863-865, P.Glafkidesd is at Chimie et Physique Photographique, and Paul Montl publishes, and 1967, G.F.Duffin is in Photographic Emulsion Chenistry, Focal Prdss publishes, and 1966, V.L.Zelikman equals Making and Coating Photographic Emulsions, Focal Press publishes, and 1964.

Be disclosed in US3,574,628 and US3,655,394, GB1,413,748 single emulsions that disperse also suit.

In addition, plain film shape particle (length-breadth ratio is at least about 3) also can be used for the present invention.Plain film shape particle can be at an easy rate with the method preparation as following document description, the Photographic Science and Engineering Vol.14 of Gutoff, P248-257(1970), US4,434,226 US4,414,3101US4,430,048 and US4,439,520 and GB2,112,157.

Crystal structure can be for uniformly, or the internal and external parts of particle can contain different halogens and form, or particle is sandwich construction, and further, the silver halide that contains different components can connect an epitaxial orientation growth part.The compound of inclusive NAND silver halide such as silver thiocyanate or massicot engages.In addition, the granulate mixture with different crystal form also can use.

Above-mentioned emulsion can be the surface latent image type that forms latent image basically on the surface, or forms the internal latent image type of latent image in particle, or a kind ofly all forms the pattern of latent image in surface and particle, but must all be negativity emulsion.To the internal latent image type, emulsion can be as being disclosed in latent image type emulsion in the nuclear/shell among the JP-A-63-264740.The preparation method of latent image type emulsion is disclosed in JP-A-59-133542 in this nuclear/shell.The selection of this emulsion thickness of the shell depends on process for developing, but 3-40nm preferably, optimum is 5-20nm.

The silver emulsion that the present invention uses will carry out physical ripening, chemical ripening and spectral sensitization effect usually.Used adjuvant is disclosed in Research Disclosure Nos.17643 in the method, and 18716 and 307105, the source of these disclosures is summarized in the table that provides below.

The grain size characteristic, the halogen of particle size distribution or photosensitive silver halide emulsion is formed, and at least a two or more different dissimilar emulsions can the form with potpourri exist in same one deck of photosensitive material of the present invention among particle form and the photographic sensitivity.

At photosensitive silver halide emulsion layer and/or basically in the non-photosensitive hydrophilic colloid layer, preferably use and be disclosed in US4,082; silver halide particle in 553 with ashing particle surface; be disclosed in US4,626,498 and silver halide particle with inner ashing or the collargol of JP-A-59-214852.Whether the silver halide particle with inner ashing particle or surperficial ashing particle is to be not limited at the exposure of photosensitive material or unexposed portion and the silver halide particle of can evenly develop (non-image form).Preparation method with silver halide particle of inner ashing or surperficial ashing is disclosed in US4, and 626,498 and JP-A-59-214852.

The kernel core/shell type silver halide particle that formation has inner ashing particle can be that single halogen is formed or different halogens is formed as the nuclear part.

But silver halide silver chloride, chlorine silver bromide, iodine silver bromide or chlorine iodine silver bromide with inner ashing or surperficial ashing particle.The size of these ashing silver halide particles does not have mandatory restriction, but mean particle size is preferred at 0.05-0.6 μ m at 0.01-0.75 μ m especially.In addition, particle form is not had mandatory restriction yet, they can be rule particles, contain polydispersion emulsion, but preferably single emulsion (wherein, amount to into weight or quantity, the magnitude range that has 95% silver halide particle at least is at ± 40% mean particle size) that disperses.

The present invention uses the silver halide of non-sensitization fine granularization to suit.Non-sensitization fine granular silver halide be become image exposure when obtaining dye image sensitization and in developing process undeveloped fine granular silver halide.The non-Photoactive silver-halide of the fine granularization of first ashing is not preferred.

The content of silver bromide can contain silver chloride and/or silver iodide to satisfy the demand from 0-100% in the fine granular silver halide.The content of silver iodide is preferred at 0.5-10mol% in the fine granular silver halide.

Fine granular silver halide mean particle size (corresponding to the mean value of view field's circle diameter) is 0.01-0.5 μ m preferably, and optimum is from 0.02 to 0.2 μ m.

The fine granular silver halide can prepare with quadrat method with common preparation Photoactive silver-halide.In the case, the surface of silver halide particle does not need optical sensibilization and spectral sensitization.Yet adding known stabilizing agent earlier before adding coating liquid is to suit as triazole, azepine indenes, benzothiazole or sulfhydryl compound or zinc compound.Collargol is also suitable to be contained in the silver halide particle layer that contains fine granularization.

All silver-colored coating weights that are contained in photosensitive material of the present invention preferably are no more than 6.0g/m ², be no more than 4.5g/m optimum ²

The active additive that is used for the known practicality of the present invention is disclosed in three pieces of above-mentioned Research Disclosure that mention, point out in following table in its source.

RD17643 RD18716 RD307105

Additive types (1978,12) (1979,11) (1989,11)

1. chemical sensitizer is 23 pages 648 pages, 866 pages on right hurdle

Film speed dose-the same-

3. spectral sensitizer and 23-24 page or leaf are 648 pages, right hurdle 866-868 page or leaf

Hypersensitizer-649 page, right hurdle

4. bleaching agent is 24 pages 647 pages, 868 pages on right hurdle

5. antifoggant and stabilizing agent 24-25 page or leaf are 649 pages, right hurdle 868-870 page or leaf

6. light absorber filters 649 pages right hurdle

Dyestuff and ultraviolet vapor 25-26 page or leaf-650 page, 873 pages on left hurdle

7. anti fouling agent is 25 pages, 650 pages on right hurdle, 872 pages on left hurdle-right hurdle

8. the dye image stabilizing agent is 25 pages 650 pages, 872 pages on left hurdle

9. hardener is 26 pages 651 pages, left hurdle 874-875 page or leaf

10. 26 pages of the same 873-874 pages or leaves of bonding agent

11. 27 pages 650 pages of plastifier and lubricants, 876 pages on right hurdle

12. coating promoter and the same 875-876 page or leaf of surfactant 26-27 page or leaf

13. 27 pages of the same 876-877 pages or leaves of antistatic agent

14. matting agent--the 878-879 page or leaf

In addition, as be disclosed in US4, in 411,987 and US4,435,503, in photosensitive material, add compound, make itself and formaldehyde reaction, prevent that with fixing formaldehyde the degeneration of the photosensitive property that caused by formaldehyde gas from suiting.

Compound in the suitable photosensitive material of the present invention comprises that those can discharge fogging agent, development accelerant, and ag halide solvent or disclosed as JP-A-1-106052, the precursor of these materials, irrelevant with the developed silver that produces in the developing process.

The dyestuff that disperses according to WO88/04794 and JP-A-1-502912 disclosed method and be disclosed in EP317,308A, US4,420,555 and the dyestuff of JP-A-1-259358 be used for photosensitive material of the present invention and suit.

Many colour couplers can be used for the present invention, and practical example is disclosed in the above-mentioned Research Disclosure.NO.17643 that mentions, VIII-C to G part, and NO.307105, the patent of being quoted in VII-C to G part.

As yellow colour former, as be disclosed in US3,933,501,4,022,620,4,326,024,4,401,752 and 4,248,961, JP-B-58-10739, GB1,425,020 and 1,476,760, US3,973,968,4,314,023 and 4,511,649, and EP249, the colour coupler among the 473A is preferred.

5-pyrazolone compounds and Pyrazoloazole compounds are preferred as magenta colour coupler, and suitable especially is as being disclosed in the compound of following document.U.S.Patents 4,310, and 619 and 4,351,897European Patent 73,636, U.S.Patents 3,061, and 432 and 3,725,067, Research Disclosure, No.24220(6,1984), JP-A-60-33552, Research Disclosure, No.24230(6,1984), Jp-A-60-43659, JP-A-61-72238, JP-A-60-35730, Jp-A-55-118034, JP-A-60-185951, U.S.Patenrs 4,500,630,4,540,654 and 4,556,630, Internarional Patent WO088/04795.

Phenols and aphthols colour coupler can be used as cyan coupler, preferably as be disclosed in those of following document:

U.S.Patents 4,052, and 212,4,146,396,4,228,233,4,296,200,2,369,929,2,801,171,2,772,162,2,895,826,3,772,002,3,758,308,4,334,011 and 4,327,173, West German Patent Laid Open 3,329,729, European Patenta 121,365A and 249,453A, U.S.Patents 3,446, and 622,4,333,999,4,775,616,4,451,559,4,427,767,4,690,889,4,254,212 and 4,296,199, JP-A-61-42658.

The colour coupler that typical polymeric dye forms is as being disclosed in US3, and 451,820,4,080,211,4,367,282,4,409,320 and 4,576,910, GB2,102,173 and EP341,188A.

Be disclosed in US4,366,237, GB2,125,570, EP96,570 and the colour coupler of West German Pathet Laid Open 3,234,533 be preferred as band look dye color coupler with a suitable diffusibleness.

The band look colour coupler of proofreading and correct the bad absorption of band look dyestuff preferably is disclosed in Research Disclosure, No.17643, VII-G part, Research Disclosure, No.307105, VII-G part, US 4,163, and 670, JP-B-57-39413, US 4,004,929 and 4,138,258, GB1,146,368.In addition, the colour coupler that use is proofreaied and correct the bad absorption of band look dyestuff by the leuco-pigment that discharges when the coupling (is disclosed in US4,774,181), and as leaving group, having the colour coupler that forms the dye matrix group of dyestuff when reacting with developer (US 4,777,120 in open) also suits.

Generation, also suits in the present invention to the colour coupler of the useful residue of sensitization when using coupling.Be disclosed in aforesaid Research Disclosure, No.17643, VII-F part, Research Disclosure, No.307105, the patent of being drawn in VII-F part, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and US 4,248,962 and 4,782,012, the DIR colour coupler that can produce development restrainer is preferred.

Be disclosed in GB2,097,140 and 2,131,188, the colour coupler of JP-A-59-157638 and JP-A-59-170840 is a preferred couplers, in developing process, it can produce with the nucleator of image form or development accelerant.In addition, as be disclosed in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687, carry out redox reaction by the oxidised form with developer and discharge fogging agent, development accelerator, the compound of ag halide solvent etc. also are suitable things.

Other compound that is used for photosensitive material of the present invention comprises: the competition colour coupler, as be disclosed in US4,130,427; Many equivalent colour couplers, as be disclosed in US4,283,472,4,338,393 and 4,310,618, be released into the DIR redox compound of toner, be released into the DIR colour coupler of toner, the DIR colour coupler of releasing redox compound, or the redox DIR of releasing redox compound is as being disclosed in JP-A-60-185950 and JP-A-62-24252, can produce dyestuff after eliminating, the recoverable colour coupler of its color is as being disclosed in EP173,302A, discharge the colour coupler of bleach boosters, as be disclosed in Research Disclosure, No.11449, No.24241, JP-A-61-201247 discharges the colour coupler of ligand, as is disclosed in US4,553,477, discharge the colour coupler of leuco dye, as be disclosed in JP-A-63-75747, discharge the colour coupler of fluorescent dye, as be disclosed in US4,774,181.

The colour coupler that uses among the present invention can be introduced photosensitive material with many known process for dispersing.

The example that can be used for the high boiling solvent of oil-water dispersibility method is disclosed in US2, and 322,027.

Under normal pressure, at least 175 ℃ of boiling points, the concrete instance that can be used for the high boiling organic solvent of oil-water dispersibility method comprises: phthalic acid ester is (as dibatyl phithalate, dicyclo-hexyl phthlate, phthalic acid two (2-ethylhexyl) ester, phthalic acid ester in the last of the ten Heavenly stems, phthalic acid two (2, the 4-di-tert-pentyl-phenyl) ester, m-phthalic acid two (2, the 4-di-tert-pentyl-phenyl) ester, phthalic acid two (1,1-diethyl propyl group) ester), the Phosphoric acid or phosphonic acid ester (as, the tricresyl phosphate benzoic acid, tricresyl phosphate, phosphoric acid-2-ethylhexyl diphenyl, the tricresyl phosphate cyclohexyl ester, tri-2-ethylhexyl phosphate, tricresyl phosphate (dodecyl) ester, tricresyl phosphate (fourth oxygen ethyl) ester, tricresyl phosphate (chloropropyl) ester, phosphonic acids two (2-ethylhexyl phenyl) ester), benzoic ether (as, benzoic acid-2-Octyl Nitrite, benzoic acid dodecane ester and P-hydroxybenzoic acid-2-ethylhexyl), acid amides (as, N, N-diethyl 12 (alkane) acid amides, N, the N-diethyl lauramide, N-myristyl pyrrolidone, alcohols or phenols (as, isooctadecane pure and mild 2, the 4-di-tert-pentyl phenol), alphatic carboxylic acid ester (for example, decanedioic acid two (2-ethylhexyl) ester, dioctyl azelate, tributyrin, lactic acid isooctadecane ester and trioctyl lemon acid), anil (as, N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline) and hydro carbons (as, alkane, dodecyl benzene, diisopropyl naphthalene), outside drawing, boiling point is higher than about 30 ℃, preferably at least 50 ℃, can be used as secondary solvent but be lower than about 160 ℃ organic solvent, the typical example of these solvents comprises: ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, acetic acid-2-ethoxy-ethyl ester and dimethyl formamide.

The process of latex process for dispersing and effect and for the actual latex example of load purpose is disclosed in US4,199,363, Deutsches Reichs-Patent application (OLS) NOs.2,541,274 and 2,541,230.

In color sensitive material of the present invention, add germifuge and biocide such as phenylethyl alcohol or 1, the 2-benzisothiazole-3-ketone, the positive butyl ester of P-hydroxybenzoic acid, phenol, 4-chloro-3,5-xylenol, 2-phenoxetol and 2-(4-thiazolyl) benzimidazole, suit, they are disclosed in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941.

The present invention can be used for various color sensitive materials.Typical example comprises: be the colour negative that use usually and process photography are used, and colour reversal film (being that lantern slide and TV are used), colour paper, colour positive and colour reversal photographic paper.

Be used for carrier that the present invention suits be disclosed in as, aforesaid Research Disclosure, No.17643,28 pages; Research Disclosure, No.18716, page left hurdle, 647 pages of right hurdles to 648 and Research Disclosure, 879 pages of No.307105.

The total film thickness of photosensitive material of the present invention all hydrophilic colloid layers on silver emulsion is laminated preferably is no more than 28 μ m, the suitable 23 μ m that are no more than, 18 μ m, the optimum 16 μ m that are no more than of being no more than preferably.In addition, film expansivity T1/2 is no more than 30 seconds aptly, optimumly is no more than 20 seconds.Film thickness is meant the film thickness of (relative humidity 55% kept two days) check weighing under 25 ℃ of conditions, and film expansivity T1/2 can record with industrial known method.As, be described in photogr.Sci.Eng. with A.Green, Vol19, No.2, the dilatometer of 124-129 page or leaf records.T1/2 is defined as half the time of film thickness that reaches capacity, and saturated film thickness refers at 30 ℃, handles material and reach 90% of maximum swelling film thickness in 3 minutes 15 seconds in colour developing solution.

Film expansivity T1/2 can be by adding the adjustment of film hardener to the gelatin of making bonding agent, perhaps by changing the aging condition after being coated with.In addition, expansion factor is that 150%-400% is preferred.Expansion factor can under above-mentioned condition or the maximum swelling film thickness, calculate with formula (maximum swelling film thickness-film thickness)/film thickness.

One side at support is the hydrophilic colloid layer (the known backing layer of doing) of 2-20 μ m with total build, and the reverse side of support then is a silver halide emulsion layer, and this suits in photosensitive material of the present invention.In backing layer with the above-mentioned light absorber of mentioning, filter dye, ultraviolet absorber, antistatic agent, hardener, bonding agent, plastifier, lubricant, coating promoter and surfactivity suit.Expansion factor in the backing layer is preferably at 150-500%.

Color photographic light-sensitive material of the present invention develops and processing with the usual method that is disclosed in following document, above-mentioned Research Disclosure, No.17643,28-29 page or leaf; Research Disclosure, No.18716,615 pages of left hurdles arrive right hurdle, Research Disclosure, No.307105,880 pages and 881 pages.

The colour developing solution that is used for the development of photosensitive material of the present invention is the color developer of principal ingredient with the alkaline aqueous solution that contains the one-level aromatic amine preferably.Aminophenols is also as color developer, but with the p-phenylenediamine (PPD) compounds is preferred, typical example comprises: 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxy ethylaniline, 3-methyl-4-ammonia-N-ethyl-N-β-methanesulfonamido ethylaniline, 3-methyl-4-amino-N-ethyl-beta-methoxy-ethylaniline, and the sulfate of these compounds, hydrochloride and tosilate.In these compounds, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline sulfate is suitable especially, and according to final purpose, two or more these compounds can be used in combination.

Colour developing solution contains pH buffering agent such as alkali carbonate usually, borate or phosphate, development restrainer or anti-photographic fog agent such as chloride bromide, iodide, benzimidazole, benzothiazoles or thiol compound.They also contain various protective agents such as azanol, diethyl hydroxylamine, sulphite as needs.Hydrazine class such as N, N-dicarboxyl methyl hydrazine, Carbaphen, triethanolamine and catechol sulfonic acid.Organic solvent such as ethylene glycol and diglycol; development accelerant such as benzylalcohol; polyglycol; quaternary amine and amine; dye color coupler; the competition colour coupler; auxiliary developer such as 1-phenyl-3-pyrrolidone; intensifier and various sequestrant; representative is the aminopolycanboxylic acid; aminopolyphosphonic acid; alkyl phosphonic acid; the phosphono carboxyl; typical example comprises: ethylenediamine tetraacetic acid; triacetamide; diethylene-triamine pentaacetic acid; CDTA; hydroxyethylamino-diacetic acid; 1-hydroxy ethylene-1; the 1-di 2 ethylhexyl phosphonic acid; nitrilo--N; N; the N-trimethylene phosphonic; ethylenediamine-N; N, N, N-tetramethylene phosphonic acid; ethylenediamine-two (o-hydroxy guanidine-acetic acid) and these sour salt.

In addition, colour development is to carry out after regular black-and-white development to reversal process.Known black-and-white development agent comprises dihydroxy benzenes class such as p-dihydroxy-benzene, and 3-pyrazolidone such as 1-phenyl-3-pyrazolidone and amino phenol such as N-methyl-para-aminophenol can be used alone or in combination in black-and-white developer.

The pH of colour and black-and-white developer is generally at 9-12.In addition, the additional speed of these developer solutions will depend on the color photographic light-sensitive material of being processed, and generally is no more than every square metre 3 liters of photosensitive materials, in replenishing liquid, by reducing bromide ion concentration, can be adjusted to and be no more than 500ml.For preventing evaporation of liquid and oxidation in the developer container, suitable is to keep minimum contact area with air, can reduce to replenish velocity of variation like this.

The contact area of sensitization working fluid can be represented with the open factor that defines below in air and the developer container:

Open factor (Open Factor)=(working fluid and air contact area (cm ²))/(working fluid volume (cm ²))

Above mentioned open factor does not preferably surpass 0.1, and optimum is 0.001-0.05.As adding a unsteady surface that is placed on sensitization working fluid in the developer container, adopt the method for floating cover to be disclosed in JP-A-1-82033 and to comprise the slot development method with isolated material, be disclosed in JP-A-63-216050, these can be used as the method that reduces open factor.Reduce open factor and not only be preferably used in colour development and the black-and-white development process, and be applicable to all subsequent processes, as bleaching, bleaching-photographic fixing, photographic fixing, washing and stabilization procedures.In addition, can reduce to replenish speed by gathering of bromide ion in the inhibition developer container.

Colour development process time is usually at 2-5 minute, but can shorten process time by the concentration that increases pH or increase color developer.

Sensitive emulsion layer is general through bleaching process after colour development.Bleaching process can and fixing (deciding in the process floating) carry out simultaneously, also can separately carry out.In addition, float and decide process and can behind bleaching process, carry out to speed operations.Moreover as needs, this process can be carried out in the bleach-fixing liquid of two connections, and fixing can carry out before deciding process floating, or bleaching process carries out after deciding process floating.Polyvalent metal compounds such as iron (III), peracid, quinones and nitro compound can be used as bleaching agent.Typical bleaching agent comprises organic complex salt of iron (III), for example, have with the complex salt of aminopolycanboxylic acid's form, aminopolycanboxylic acid's example: ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, CDTA, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycerin ether two amido tetraacethyl or citric acid, tartrate or maleic acids.In these raw materials, using polyamino ferric carboxylate (III) complex salt, mainly is ethylenediamine tetraacetic acid iron (III) complex salt and 1, and 3-diaminopropanetetraacetic acid iron (III) complex salt is preferred, and their processes that can speed operations prevent the pollution of the environment.In addition, amido polycarboxylic acid ferric (III) complex salt is specially adapted to bleaching liquid and bleach-fixing liquid.The pH value of using the bleaching liquid of these amido polycarboxylic acid ferrics (III) salt and bleach-fixing liquid is usually at 4.0-8, but available low pH value is to accelerate process velocity.

As needs, can be at bleaching liquid, bleach-fixing liquid or bleaching or float surely in the pre-liquid and use bleach boosters.Use the example of bleach boosters to be disclosed in following publication.Like this, contain sulfydryl or the disulfide group compounds is disclosed in: US3,893,858, DE1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, J-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure, No.17129(7,1978); Tetrahydrothiazole derivates is disclosed in JP-A-50-140129; Thiourea derivative is disclosed in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US3, and 706,561, the iodide salt is disclosed in DE1, and 127,715 and JP-A-58-16235; The polyoxyethylene compounds is disclosed in DE966, and 410 and 2,748,430; Polyamine compound is disclosed in JP-B-45-8836; Other compounds is disclosed in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; And bromide ion.In these compounds, the compound that contains sulfydryl or disulfide group is preferred because of its big facilitation, is disclosed in US3,893,858, DE1,290,812 and the compound of JP-A-53-95630 be suitable especially.In addition, be disclosed in US4,552,834 compound also suits.These bleach boosters can be added in the photosensitive material.These bleach boosters are especially effective to floating the color sensitive material of taking pictures surely.

Adding organic acid and compound above-mentioned suit in bleaching liquid and bleach-fixing liquid, to avoid bleaching the generation of pollution.It is suitable especially from the compound of 2-5 that organic acid is had acid dissociation constant (pKa), in fact, is preferred as acetate and propionic acid.

Thiosulfate, thiocyanate, thio-ether type compounds, thiocarbamide and most iodide can be used as the fixer that makes as in stop bath or the bleach-fixing liquid, but thiosulfate is to adopt usually, ATS (Ammonium thiosulphate) especially can be used in very on a large scale.In addition, thiosulfate and thiocyanate, sulfide compound, thiocarbamides etc. are used in combination also and suit.Be disclosed in EP294, the sulphite of 769A, hydrosulfite, carbonyl/bisulfite addition product or sulfinic acid compound preferably are used as the protective agent of stop bath and bleach-fixing liquid.And, in stop bath and bleach-fixing liquid, add different aminopolycanboxylic acid and organic phospho acid, it is stablely also suited.

In the present invention, the compound 0.1-10mol/l that adds pKa and be 6.0-9.0 in stop bath or bleach-fixing liquid suits with control pH, and these compounds are glyoxaline compound such as imidazoles, 1-methylimidazole, 1-ethyl imidazol(e) and glyoxal ethyline preferably.

In the scope that desilverization failure does not take place, it is preferred that short total desilverization processing time is arranged.Preferably 1-3 minute desilverization time, optimum is 1-2 minute.And processing temperature is at 25 °-50 ℃, preferably from 35-45 ℃.In preferred temperature range, can increase desilverization speed, can antipollution effectively generation after the processing.

Suitable in the desilverization process strong agitation as much as possible.The example of strong agitation method comprises: as be disclosed in the method for JP-A-62-183460, wherein the jet with treat liquid directly impacts photosensitive material emulsion surface: as the method that is disclosed in JP-A-62-183461 wherein increases mixing effect with whirligig, with contacting with the emulsion surface, be placed in wide blade in the liquid and move the method for photosensitive material, produce turbulence and increase mixing effect on the emulsion surface like this, on the whole the method for the circulation velocity of working fluid increase.These increase stirring method at bleaching liquid, are effective in bleach-fixing liquid and the stop bath.Can imagine that having increased to stir has promptly increased the feed speed of bleaching agent and fixer to the emulsion film, thereby has also increased desilverization speed.In addition, above-mentioned increase stirring method is more effective under the situation of using bleach boosters, increases to stir and can significantly improve facilitation effect, eliminates the fixer inhibiting effect that is caused by bleach boosters.

The automatic film developer that is used to handle photosensitive material of the present invention preferably has as being disclosed in the photoelement transfer appts of JP-A-60-191257, JP-A-60-191258 or JP-A-60-191259.By means of this conveyer (as being disclosed in above-mentioned JP-A-60-191257), the working fluid that carries during from a kind of body lotion to following a kind of body lotion will significantly reduce, and it also can prevent the degeneration of working fluid performance effectively.This effect especially to the shortening of process time of every kind of process and every kind of working fluid replenish speed to reduce be useful.

Silver halide color photographic light-sensitive material of the present invention usually will be through washing processing and/or stabilization processing after the desilverization is handled.The quantity that is used for washing processing water can be selected in a very wide scope, depend on concrete application and photosensitive material character (as, depend on material as being contained in the colour coupler in the photosensitive material) washing water temperature, water washing chamber number (washing stage number) and additional system, promptly, whether adopt adverse current or continuous stream system, and other condition.Make the pass between the number of the quantity of water and washing box tie up to available journal of the Society of Motion Picture and Television Engineer in the multistage counter current system, Vol.64(5,1955) the listed method acquisition of 248-253 page or leaf.

Can significantly reduce the quantity of washings with the multistage counter current system of above-mentioned document description, but by the increase of hold-up time of water in case and cause the breeding of bacterium.Along with generation, also produced problem to photosensitive material aggregation suspension.When processing color sensitive material of the present invention, the method that reduces calcium ion and magnesium ion concentration of using as be disclosed in JP-A-62-288838 is to overcome this problem efficient ways.In addition, isothiazolone compounds class and thiabendazoles(are disclosed in JP-A-57-8542), chlorine-containing disinfectant such as chlorinated isocyanuric acid sodium, benzotriazole and the TheChemistry of Biocides and Fungicides(1986 that is disclosed in Horiguchi, Sankyo Shuppan), Killing Microorganisms, Biocidal and Fungicidal Techniques(1982), The Health and Hygiene Technology Society publish, the A Dictionay of Biocides and Fungicides(1986 that is published by the Japanese Biocide and Fungicide Society) sanitizer also can be used for this purpose.

Processing photosensitive material of the present invention, the pH value of washings is 4-9, preferably 5-8.Character and application that the water temperature of washing and wash time depend on photosensitive material, but washed 20 seconds-10 minutes under wash conditions is selected at 15 °-45 ℃ usually, preferably 25 °-40 ℃ were washed 30 seconds-5 minutes.In addition, photosensitive material of the present invention can directly be processed in stabilizing solution and not need process as above-mentioned washing.The known method that is disclosed in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used as this stable processing.

Moreover, also there is stable processing to be next to situation after the above-mentioned washing processing, contain as the stabilizing solution of final dye stabilizers of bathing of photograph color sensitive material and surfactant a example as this method.Aldehydes such as formalin and glutaraldehyde, N-hydroxymethyl quasi-compound, hexamethylene tetramine and aldehyde/bisulfite addition product can be used as dye stabilizers and use.

Various sequestrants and germifuge also can be added in these stabilizing solutions.

The overflow of following above-mentioned washing or stabilizing solution to replenish is reusable in other processing, as in desilverization processing.

When with the automatic processor machine work, because evaporation is when making above-mentioned working fluid retrogradation, usefulness adds water and revises concentration and suit.

Color developer can be incorporated in the silver-halide color photoelement of the present invention, to simplify and the acceleration process.The combination of different color developer parents is preferred.For example, the indenes amino benzenes compounds (is disclosed in US3,342,579), be disclosed in US3,342,599, Research Disclosure, No.14850 and Research Disclosure, the Schiff of No.15159 (the bases compound of Schiff ' s), be disclosed in Research Disclosure, the 3-hydroxybutyraldehyde of No.13924 is disclosed in US3,719,492 metal complex salt class and all available this purpose of urethane ester type compound that is disclosed in JP-A-53-135628.

As needs, various 1-phenyl-3-pyrazolidone can be incorporated photosensitive silve halide material of the present invention into to accelerate colour development.The example of typical compound is disclosed in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Various working fluid of the present invention uses down at 10 °-50 ℃.Standard temperature still is appreciated that when high temperature usually at 33 °-38 ℃, can quicken processing, shortens process time, and on the other hand, can improve the quality of photo at low temperatures, and working fluid also has stability preferably.

In addition, photosensitive silve halide material of the present invention also can be used as heat-developed photosensitive material, as is disclosed in US4, and 500,626, JP-A-60-133449, JP-A-59-218443, J-A-61-238056 and EP210,660A.

Describe the present invention by following case illustrated, but cannot limit the present invention by these examples.

Embodiment 1

Dissolving 30 gram inertia gelatin and 6 gram potassium bromides obtain aqueous gelatin solution in 1 liter of distilled water.Stir down at 75 ℃, to wherein with the speed of 70cc/min, in 30 seconds, add 35cc simultaneously and contain the 5.0 gram aqueous solution of silver nitrates and 35 milliliters of aqueous solution that contain 3.2 gram potassium bromides and 0.98 gram potassium iodide, treat to obtain crystal seed emulsion after the PAg value reaches 10, with carrying out maturation in 30 minutes.

Then, every liter of aqueous solution that contains potassium bromide and potassium iodide potpourri that contains 145 gram 50 ml water solution of silver nitrates and equimolar amounts 65 ℃ of addings wherein adds speed near critical growth rate, and the PAg value is 12, obtains flat dull and stereotyped nuclear emulsion like this.Being different from the potassium bromide of the remaining silver nitrate aqueous solution for preparing dull and stereotyped nuclear emulsion and equimolar amounts and the aqueous solution of potassium iodide potpourri then adds with the adding speed that is bordering on critical growth rate.Dull and stereotyped nuclear part is capped and obtains dull and stereotyped core/shell type plain film shape iodine silver bromide emulsion 1-5, and is as follows.

By selecting PAg value (obtaining in the emulsion process at dull and stereotyped nuclear of preparation and shell) to control the form ratio, gained emulsion is shown among the table 1-1.

Table 1-1

Average average average iodine

The average average form grain of form diameter grain thickness thing content

Emulsion * ratio ¹Ratio ²(μ m) (μ m) (mol%)

1 1.5/1 1.2/1 0.86 0.67 7.6

2 2.8/1 2.2/1 1.01 0.55 7.6

3 4.6/1 3.6/1 1.63 0.36 7.6

4 6.7/1 5.2/1 1.74 0.30 7.6

5 11.7/1 9.8/1 2.10 0.21 7.6

1): tested 1000 emulsion grains, recorded the form ratio of each particle.Select to calculate the particle of total projection area 50% from the particle that big form ratio is arranged, its mean value is the formation ratio of these particles.

2): this is as above-mentioned 1) in the mean value of particle shape ratio that total projection area 85% is calculated.

*: the iodide content of emulsion 1-5 particle is 0% at flat board nuclear, is 8mol% on shell.

Then, each layer with the composition that indicates below, made bottom thereon and contained 0.05 gram/rice to the cellulose triacetate membrane carrier by multi-layer coated ²Gelatin and 0.01 gram/rice ²Phenol is with preparation multilayer photosensitive material sample 101.

Photographic layer is formed

Digital value corresponding to each component is represented with g/m ²Be the coating weight of unit, the coating weight of informing is then as the calculated weight of silver emulsion silver.In addition, to photosensitizing dye, coating weight is the molar weight unit representation that is used in every mole of silver halide on one deck.

Sample 101

Ground floor: antihalation layer

Black collargol 0.18 is in silver

Gelatin 1.40

The second layer: middle layer

2.5-two uncles-pentadecyl quinhydrones 0.18

EX-1 0.070

EX-3 0.020

EX-12 2.0×10 ^-3

U-1 0.060

U-2 0.080

U-3 0.10

HBS-1 0.10

HBS-2 0.020

Gelatin 1.04

The 3rd layer: the first magenta-sensitive emulsion layer

Emulsion A 0.25 is in silver

Emulsion B 0.25 is in silver

Sensitizing dye I 6.9 * 10 ^-5

Sensitizing dye II 1.8 * 10 ^-5

Sensitizing dye III 3.1 * 10 ^-4

EX-2 0.34

EX-10 0.005

EX-14 0.030

U-1 0.070

U-2 0.050

U-3 0.070

HBS-1 0.060

Gelatin 0.87

The 4th layer: the second magenta-sensitive emulsion layer

Emulsion G 1.00 is in silver

Sensitizing dye I 5.1 * 10 ^-5

Sensitizing dye II 1.4 * 10 ^-5

Sensitizing dye III 2.3 * 10 ^-4

EX-2 0.40

EX-3 0.050

EX-10 0.005

EX-14 0.030

U-1 0.070

U-2 0.050

U-3 0.070

Gelatin 1.30

Layer 5: the 3rd magenta-sensitive emulsion layer

Emulsion 1 1.60 is in silver

Sensitizing dye I 9.5 * 10 ^-5

Sensitizing dye II 3.0 * 10 ^-5

Sensitizing dye III 5.0 * 10 ^-4

EX-2 0.097

EX-3 0.010

EX-4 0.080

EX-10 0.005

EX-14 0.020

The compound (11) 3.0 * 10 that illustrates ^-4

HBS-1 0.22

HBS-2 0.10

Gelatin 1.63

Layer 6: middle layer

EX-5 0.040

HBS-1 0.020

Gelatin 0.80

Layer 7: the first green-sensitive emulsion layer

Emulsion A 0.15 is in silver

Emulsion B 0.15 * in silver

Sensitizing dye IV 3.0 * 10 ^-5

Sensitizing dye V 1.0 * 10 ^-4

Sensitizing dye VI 3.8 * 10 ^-4

EX-1 0.021

EX-6 0.26

EX-7 0.030

EX-8 0.025

HBS-1 0.10

HBS-3 0.10

Gelatin 0.63

The 8th layer: the second green-sensitive emulsion layer

Emulsion C 0.45 is in silver

Sensitizing dye IV 2.1 * 10 ^-5

Sensitizing dye V 7.0 * 10 ^-5

Sensitizing dye VI 2.6 * 10 ^-4

EX-6 0.094

EX-7 0.026

EX-8 0.018

HBS-1 0.16

HBS-3 8.0×10 ^-3

Gelatin 0.50

The 9th layer: the 3rd green-sensitive emulsion layer

Emulsion 1 1.20 is in silver

Sensitizing dye IV 5.0 * 10 ^-5

Sensitizing dye V 1.0 * 10 ^-4

Sensitizing dye VI 4.0 * 10 ^-4

EX-1 0.025

EX-11 0.10

EX-13 0.015

Compound (18) 5.0 * 10 is described ^-4

HBS-1 0.25

HBS-2 1.0

Gelatin 1.54

The tenth layer: the Yellow filter layer

Yellow colloidal silver 0.050 is in silver

EX-5 0.080

HBS-1 0.030

Gelatin 0.95

Eleventh floor: the first blue-sensitive emulsion layer

Emulsion A 0.080 is in silver

Emulsion B 0.070 is in silver

Emulsion F 0.070 is in silver

Sensitizing dye VII 3.5 * 10 ^-4

EX-8 0.042

EX-9 0.72

HBS-1 0.28

Gelatin 1.10

Floor 12: the second blue-sensitive emulsion layer

Emulsion G 0.45 is in silver

Sensitizing dye VII 2.1 * 10 ^-4

EX-9 0.15

EX-10 7.0×10 ^-3

HBS-1 0.050

Gelatin 0.78

The 13 layer: the 3rd blue-sensitive emulsion layer

Emulsion H 0.77 is in silver

Sensitizing dye VII 2.2 * 10 ^-4

EX-9 0.20

HBS-1 0.070

Gelatin 0.69

The 14 layer: first protective seam

Emulsion I 0.20 is in silver

Compound (18) 1.0 * 10 is described ^-4

U-4 0.11

U-5 0.17

HBS-1 5.0×10 ^-2

Gelatin 1.00

The 15 layer: second protective seam

H-1 0.40

B-1(diameter: 1.7 μ m) 5.0 * 10 ^-2

B-2(diameter: 1.7 μ m) 0.10

B-3 0.10

S-1 0.20

Gelatin 1.20

In addition, W-1, W-2, W-3, B-4, B-5, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, and molysite, lead salt, golden salt, platinum salt, iridium salt and rhodium salt are contained in each layer to improve storage character, working properties, resistance to compression, sterilization and biocidal properties and coating character.

The change diameter/thickness silver part by weight of average A gI average grain bulky grain size

Emulsion content (%) little (μ m) is changed coefficient (%) ratio (AgI content %)

A 4.0 0.45 27 1.2 nuclear/shells=1/3(13/1),

The double structure particle

B 8.9 0.70 14 1.2 nuclear/shells=3/7(25/2),

The double structure particle

C 10 0.75 30 1.5 nuclear/shells=1/2(24/3),

The double structure particle

D 16 1.05 35 1.8 nuclear/shells=4/6(40/0),

The double structure particle

E 10 1.05 35 1.8 nuclear/shells=1/2(24/37),

The double structure particle

F 4.0 0.25 28 1.5 nuclear/shells=1/3(13/1),

The double structure particle

G 14.0 0.75 25 1.5 nuclear/shells=1/2(42/0),

The double structure particle

H 14.5 1.30 25 1.9 nuclear/shells=37/63(34/3),

The double structure particle

I 1 0.70 15 1.0 single-sizes

Sample 102-105

Sample 102-105 replaces the emulsion 1 in the 5th and the 9th layer of sample 101 to make respectively with emulsion 2-5

Sample 106-125

The preparation of sample 106-125 is to add yellow cyan colour coupler of the present invention (YC-1) among the sample 101-105 respectively, (YC-28), and (YC-44) or (YC-47), 1-2 represents as following table, with 0.015g/m ²Amount be added to the 3rd layer, the 4th adds 0.030g/m ², layer 5 is 0.030g/m ²

Sample 126-130

The preparation of sample 126-130 is compound (11) and (18) of saving general formula of the present invention (A) representative, and they once were added into the 5th and the 9th layer and the 14 layer of sample 111-115 respectively.

As following, add the preparation that (YC-28) comprises emulsifying dispersant in the method for the 4th layer in sample 111.

The W-3 of ox bone gelatin (60g) and 2g is added in the 800ml water, 50 ℃ of dissolvings down.In addition, EX-2(40g), EX-3(5g), EX-10(0.5g), EX-14(3g), U-1(7g), U-2(5g), U-3(7g), W-2(3g) and YC-28(3g) in 60 ℃ of ethyl acetate that are dissolved in 150ml, mix with above-mentioned aqueous gelatin solution with a family expenses blending bin, emulsification is 10 minutes in blending bin, obtain a spreading agent, it is mixed with emulsion.

Yellow cyan colour coupler is added to other layer and the interpolation of other yellow colour coupler is carried out in same mode.

The sample that makes like this will become image exposure and colour development, its mode such as following through white light.The following commentary valency of the sample of Chu Liing like this, it the results are shown in table 1-2.The logarithm that provides the exposure inverse of (photographic fog+0.2) cyan density is listed in table 1-2 as relative velocity.

In addition, be that the RMS value of (photographic fog+0.5) blue or green optical density of recording of the hole of 48 μ m sees Table 1-2 with diameter.

And, obtain the mtf value of 40 weeks/mm cyan image.Its survey method is with The Theory of the photographic process, the 3rd edition method that (Mees, Macmillan publishes) describes.

In addition, the value that yellow density in the yellow density amount of being exposed in the cyan Fog density deducts gained sees Table 1-2 as the degree of color turbidity, described exposure is meant (fog+1.5) cyan density that obtains through red imaging exposure again after sample is through even blue exposure (0.3LukSec is through the BPN-45 optical filter of Fuji Photo Film Co.Ltd. manufacturing).

And sample also will be through the white light exposure of 10LuxSec., colour development and process with the bleaching time of 30 minutes or 2 minutes.

The value that the fuchsin density that the fuchsin density of bleaching 30 minutes was bleached 2 minutes deducts sees Table 1-2 as the not enough density of the desilverization.

At 38 ℃, carry out colour development processing with following operating conditions,

Colour development 3 minutes and 15 seconds

Bleach 30 minutes (or 2 minutes)

Washed 2 minutes and 10 seconds

Photographic fixing 4 minutes and 20 seconds

Washed 3 minutes and 15 seconds

Stablized 1 minute and 05 second

The indication of the composition of used working fluid is as follows in every kind of process.

Color developer

Diethylene-triamine pentaacetic acid 1.0g

1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid 2.0g

Sodium sulphite 4.0g

Sal tartari 30.0g

Potassium bromide 1.4g

Potassium iodide 1.3mg

Hydroxylamine sulfate 2.4g

4-(N-ethyl-N-beta-hydroxyethyl amino)

-2-aminotoluene sulfate 4.5g

Add water to 1.0 liters

pH 10.0

Bleaching agent

Ethylene diaminetetraacetic acid iron (III) ammonium salt 100.0g

Ethylene diaminetetraacetic acid disodium salt 10.0g

Ammonium bromide 150.0g

Ammonium nitrate 10.0g

Add water to 1.01

pH 6.0

Fixer

Ethylene diaminetetraacetic acid disodium salt 1.0g

Sodium sulphite 4.0g

Thiosulfuric acid aqueous ammonium (70wt%) 175.0ml

Sodium bisulfite 4.6g

Add water to 1.0 liters

pH 6.6

Stabilizing agent

Formalin (40wt%) 2.0ml

Polyoxyethylene-right-single nonylplenyl ether is (average

The degree of polymerization: 10) 0.3g

Add water to 1.01

Table 1-2

Sample the 5th, nine yellow blue or green formulas (A) are represented relative sensitivity

The compound of emulsion colour coupler in the layer

101(is relatively) 1-(11)/(18) 0.00

102(is relatively) 2-(11)/(18) 0.00

103(is relatively) 3-(11)/(18) 0.02

104(is relatively) 4-(11)/(18) 0.03

105(is relatively) 5-(11)/(18) 0.04

106(is relatively) 1 YC-1 (11)/(18) 0.03

The 107(invention) 2 YC-1 (11)/(18) 0.04

The 108(invention) 3 YC-1 (11)/(18) 0.05

The 109(invention) 4 YC-1 (11)/(18) 0.06

The 110(invention) 5 YC-1 (11)/(18) 0.07

111(is relatively) 1 YC-28 (11)/(18) 0.03

The 112(invention) 2 YC-28 (11)/(18) 0.03

The 113(invention) 3 YC-28 (11)/(18) 0.05

The 114(invention) 4 YC-28 (11)/(18) 0.06

The 115(invention) 5 YC-28 (11)/(18) 0.07

Table 1-2(is continuous)

Sample RMS value * mtf value, the color turbidity desilverization of cyan deficiency

1,000 look image, 40 all density

101(is relatively) 30.3 0.40 0.06 0.08

102(is relatively) 29.5 0.43 0.08 0.12

103(is relatively) 29.0 0.45 0.09 0.14

104(is relatively) 28.8 0.45 0.09 0.15

105(is relatively) 28.7 0.45 0.09 0.15

106(is relatively) 30.6 0.41-0.08 0.03

The 107(invention) 29.7 0.44-0.06 0.04

The 108(invention) 29.1 0.46-0.05 0.05

The 109(invention) 28.9 0.46-0.05 0.05

The 110(invention) 28.7 0.46-0.05 0.06

111(is relatively) 30.5 0.41-0.08 0.03

The 112(invention) 29.6 0.44-0.06 0.04

The 113(invention) 29.0 0.46-0.05 0.05

The 114(invention) 28.9 0.46-0.05 0.05

The 115(invention) 28.7 0.46-0.05 0.06

Table 1-2(is continuous)

Sample the 5th, nine yellow blue or green formulas (A) are represented relative sensitivity

The compound of emulsion colour coupler in the layer

116(is relatively) 1 YC-44 (11)/(18) 0.02

The 117(invention) 2 YC-44 (11)/(18) 0.03

The 118(invention) 3 YC-44 (11)/(18) 0.04

The 119(invention) 4 YC-44 (11)/(18) 0.05

The 120(invention) 5 YC-44 (11)/(18) 0.06

121(is relatively) 1 YC-47 (11)/(18) 0.02

The 122(invention) 2 YC-47 (11)/(18) 0.02

The 123(invention) 3 YC-47 (11)/(18) 0.04

The 124(invention) 4 YC-47 (11)/(18) 0.04

The 125(invention) 5 YC-47 (11)/(18) 0.05

126(is relatively) 1 YC-28-0.01

The 127(invention) 2 YC-28-0.02

The 128(invention) 3 YC-28-0.03

The 129(invention) 4 YC-28-0.04

The 130(invention) 5 YC-28-0.05

Table 1-2(is continuous)

The not enough density of sample RMS value * mtf value color turbidity desilverization

1,000 40 week

116(is relatively) 30.6 0.41-0.06 0.03

The 117(invention) 29.7 0.44-0.04 0.04

The 118(invention) 29.1 0.46-0.03 0.05

The 119(invention) 29.0 0.46-0.03 0.05

The 120(invention) 28.9 0.46-0.03 0.06

121(is relatively) 30.5 0.40-0.04 0.04

The 122(invention) 29.6 0.43-0.02 0.05

The 123(invention) 29.1 0.45-0.01 0.06

The 124(invention) 29.0 0.45-0.01 0.06

The 125(invention) 28.8 0.45-0.01 0.07

126(is relatively) 31.3 0.41-0.08 0.07

The 127(invention) 30.2 0.44-0.06 0.08

The 128(invention) 29.5 0.46-0.05 0.08

The 129(invention) 29.3 0.46-0.05 0.09

The 130(invention) 29.2 0.46-0.05 0.09

From table 1-2, sample of the present invention is obviously compared with the sample 102-105 that does not have yellow cyan colour coupler, shows higher photographic sensitivity, the not enough density of the color rendition of representing with the color turbidity, and the lower desilverization preferably.In addition, sample of the present invention and the comparative sample 106,111,116 that contains the emulsion 1 that exceeds scope of the invention form ratio are compared with 121 and are shown higher photographic sensitivity, graininess and sharpness preferably.

In addition, the sample 112-115 that contains formula (A) representation compound clearly illustrates that, compares with the comparative sample 127-130 that does not contain formula (A) representation compound, and they show higher photographic sensitivity, and graininess and sharpness preferably.

Example 2

Emulsion 6(the present invention)

2M contains the silver nitrate aqueous solution of gelatin and 2M and contains the kbr aqueous solution of gelatin (every kind solution in 25cc) at 30 ℃, in 1 minute, swashing thermal agitation mixes in 1 liter of 0.7wt% gelatin solution that contains the 0.04M potassium bromide down simultaneously, then, temperature rises to 75 ℃, adds the 300cc10wt% aqueous gelatin solution.Then, added the 30cclM silver nitrate aqueous solution in 5 minutes, add the 10cc25wt% ammonia solution again, potpourri is 75 ℃ of maturations.After the maturation of waiting is finished, neutralize ammonia, with the method for accelerating flow velocity (when the flow velocity of Jia Ruing is beginning at last five times), keeping pBr value is 2.3, and the while is 1M silver nitrate aqueous solution and the mixing of 1M kbr aqueous solution.(amount of used silver nitrate aqueous solution is 600cc.).Emulsion, adds and disperses to use gelatin with water washing with flocculence, obtains 800g hexagonal plain film silver emulsion (crystal seed emulsion A).This crystal seed emulsion A is averaging projection's area of 1.0 μ m by corresponding circle diameter (grain size), and average thickness is 0.18 μ m, and variation factor is single hexagonal plain film particle composition that disperses of 11%.Then, in this crystal seed emulsion of 250g A, add 800cc distilled water, 30g gelatin and 6.5g potassium bromide, be warming up to 75 ℃, stir down and simultaneously 1M silver nitrate aqueous solution and 1M alkali metal halide aqueous solution (potpourri of the potassium bromide of 90mol% and 10mol% potassium iodide) are mixed, accelerate flow velocity (when final flow rate is beginning three times), keeping the pBr value is 1.6.(using the amount of silver nitrate aqueous solution to be 600c).In addition, with the flow velocity accelerated (when final flow rate is beginning 1.5 times) 1M silver nitrate aqueous solution and 1M kbr aqueous solution are mixed simultaneously, keeping the pBr value is 1.6.(amount of the silver nitrate aqueous solution that uses is 200cc).

The emulsion of gained is wet concentration in the above described manner, adds to disperse to use gelatin, obtains single tabular silver emulsion of hexagonal (emulsion 6) that disperses.92% of the emulsion 6 total projection areas of Huo Deing thinks hexagonal plain film shape particle like this, and its mean particle size is 1.75 μ m, and average particle thickness is 0.29 μ m, and average form ratio is 6: 1, and variation factor is 16%.

Emulsion 7(the present invention)

Crystal seed emulsion B obtains with crystal seed emulsion A the same manner of emulsion 6, and the amount of the 1M silver nitrate that different is adds for the second time is 20cc, and the dosage of ammoniacal liquor is 8cc.Then, be 1.5 except keeping the pBr value growth period, with the emulsion 6 identical modes emulsion B that grows.90% of the total projected area of the emulsion of Huo Deing thinks hexagonal plain film particle like this, and its mean particle size is 2.1 μ m, and average thickness is 0.21 μ m, and average form ratio is 10: 1, and variation factor is 19%.

Emulsion 8(the present invention)

The consumption that adds for the second time silver nitrate in the preparation emulsion 6 is become 10cc from 30cc, add the fashionable ammonia spirit that do not add for the third time, pBr value is become 1.7 from 2.3, obtain crystal seed emulsion c like this, then, emulsion c is grown, obtain emulsion 8 with the method for emulsion 6 uses.

62% of the total projected area of the emulsion of Huo Deing thinks hexagonal plain film particle like this, and its mean size is 2.0 μ m, and average thickness is 0.17 μ m, and average form ratio is 12: 1, and variation factor is 37%.

The sensitizing dye I, II, III and IV were with mol ratio 0.2: 0.05: 1: 0.3 mixes, institute's dosage equals 70% of each emulsion 6,7,8 and 1 saturated extent of adsorption, keep potpourri in 60 ℃ after 20 minutes, at 60 ℃ of pH is 6.5 o'clock, uses sodium thiosulfate, and gold chloride and potassium rhodanide carry out optimal chemical sensitization effect respectively.(emulsion 6-1,7-1,8-1 and 1-1).

Table 2-1

AgI content between average average the big hexagonal plain film of the particle particle

The average little variation ratio of the big granule thickness of the average form grain of the average form of form ⁴⁾Relative standard deviation ⁵⁾

The emulsion ratio ¹⁾Ratio ²⁾Ratio ³⁾(μ m) (μ m) coefficient (%) (%)

6-1 7.9/1 7.2/1 6.0/1 1.75 0.29 0.15 92 13

7-1 13/1 11/1 10/1 2.10 0.21 0.19 90 16

8-1 21/1 17/1 12/1 2.00 0.17 0.37 62 24

1-1 1.5/1 1.2/1 1.1/1 0.86 0.67 0.25 10 22

1), 2): by showing the value that 1-1 the same manner records.

3): the mean value of all particles.

4): the emulsified particles total projection area ratio of thinking the sexangle particle.

5): based on the JP-A-60-143332 measured value.

Sample 201-204

The preparation of sample 201-204 be with the emulsion in the layer 5 of sample 101 1 respectively with emulsion 6-1,7-1,8-1 and 1-1 replace and get.

Sample 205-220

The preparation of sample 205-220 is by adding yellow cyan colour coupler of the present invention (YC-26) respectively in sample 201-204, (YC-27), (YC-30) or (YC-31) obtaining, and shown in following table 2-2, its amount is: second layer 0.010g/m ², the 3rd layer of 0.015g/m ², the 4th layer of 0.050g/m ², layer 5 0.010g/m ²

Make the relative sensitivity of sample like this, the RMS value, mtf value and color turbidity are estimated with the mode that is same as example 1, and it the results are shown in table 2-2.Yet, the colour development method of employing such as following.

Develop with egative film automatic film developer flushing operation, it is as follows that working fluid is formed indication:

But the evaluation of sample is after the sample imaging exposure of processing, carries out when the magnitude of recruitment of color developer reaches three times of mother liquor tankages.

Process operation

Processing processing temperature process time is replenished speed * tankage

（℃） （ml） （l）

Colour development 3min 15sec 38.0 23 15

Bleaching 50sec 38.0 55

Float and decide 50sec 38.0-5

Photographic fixing 50sec 38.0 16 5

Washing (1) 30sec 38.0-3

Washing (2) 20sec 38.0 34 3

Stablize 20sec 38.0 20 3

Dry 1min 55

* the additional speed of every meter of the wide material of 35mm.

Washing uses from (2) to (1) counter current system to carry out, and the overflow washing all is incorporated into stop bath.By in automatic film developer, carry out bleach-fixing liquid and replenish in connecting guide box between the bottom of the top of bleaching liquid and bleach-fixing liquid case and between the bottom of the top of stop bath case and bleach-fixing liquid case.All all introduce the bleach-fixing liquid case by the overflow that bleaching liquid case and stop bath case produce.In addition, the development liquid measure of being detained in the bleaching processing is floated the bleaching liquid measure of deciding to be detained in the processing, and the photographic fixing liquid measure is respectively per 1 meter long in bleach-fixing liquid amount of being detained in the photographic fixing processing and the washing processing, 35 mm wide photosensitive material 2.5ml, 2.0ml, 2.0ml and 2.0ml.And under every kind of situation, the intersection time is 5 seconds, is included in the process time of prebath during this period of time.According to the JP-A-62-183460 disclosed method, every kind of working fluid is provided by the device that can produce working fluid jet impulse photosensitive emulsion surface.

Working fluid is composed as follows:

Developer tank solution replenishes liquid

Diethylene-triamine pentaacetic acid 2.0g 2.2g

1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid 3.3g 3.3g

Sodium sulphite 3.9g 5.2g

Sal tartari 37.5g 39.0g

Potassium bromide 1.4g 0.4g

Potassium iodide 1.3mg-

Hydroxylamine sulfate 2.4g 3.3g

2-methyl-4-[N-ethyl-N-

(beta-hydroxyethyl amino] aniline sulfate 4.5g 6.1g

Add water to 1.0liter 1.0liter

pH 10.05 10.15

Bleaching agent case solution replenishers

1,3-trimethylene diamine tetraacethyl,

-hydrated iron (III) ammonium 144.0g 206.0g

Ammonium bromide 84.0g 120.0g

Ammonium nitrate 17.5g 25.0g

Glycolic 63.0g 90.0g

Acetate 33.2g 47.4g

Add water to 1.0liter 1.0liter

pH 3.20 2.80

(regulating) with ammoniacal liquor

Bleach-fixing liquid case solution:

The potpourri of 15: 85 above-mentioned bleaching case solution and fixer case solution is described below:

Fixer case solution replenishes liquid

Ammonium sulfite 19.0g 5.70g

Thiosulfuric acid aqueous ammonium (700g/l) 280ml 840ml

Imidazoles 28.5g 85.5g

Ethylene diaminetetraacetic acid 12.5g 37.5g

Add water to 1.0liter 1.0l

pH 7.40 7.45

(use ammoniacal liquor, acetate is regulated)

The water of washing

Make the city fill out water by using H-type storng-acid cation exchange resin (the Pohm ﹠amp; Haas Co, " the Amberlite IR-120B " that produces) and the mixing column of OH-type strong-base anion-exchange resin (" Amberlite IRA-400 " that same company produces) filling, make calcium ion and magnesium ion concentration respectively be no more than 3mg/l, after this add the dichloride isocyanuric acid sodium of 20mg/l and the sodium sulphate of 150mg/l.The pH of washings is in the 6.5-7.5 scope.

Fixer (case solution equals to replenish liquid)

Formalin (37wt%) 2.0ml

The single nonyl phenyl of polyoxyethylene-P-

Ether (average degree of polymerization: 10) 0.3g

Table 2-2

Layer 5 RMS value

The yellow cyan coupler relative sensitivity of emulsion X1 in the sample, 000 mtf value color turbidity

201(is relatively) 6-1-0.00 27.4 0.43 0.11

202(is relatively) 7-1-0.03 27.9 0.43 0.11

203(is relatively) 8-1--0.05 28.5 0.43 0.11

204(is relatively) 1-1--0.08 29.8 0.41 0.07

The 205(invention) 6-1 YC-26 0.03 27.6 0.44-0.02

The 206(invention) 7-1 YC-26 0.06 28.1 0.44-0.02

The 207(invention) 8-1 YC-26-0.02 28.7 0.44-0.02

208(is relatively) 1-1 YC-26-0.05 30.0 0.42-0.05

The 209(invention) 6-1 YC-27 0.03 27.6 0.44-0.02

The 210(invention) 7-1 YC-27 0.06 28.0 0.44-0.02

The 211(invention) 8-1 YC-27-0.02 28.6 0.44-0.02

212(is relatively) 1-1 YC-27-0.05 30.0 0.42-0.05

The 213(invention) 6-1 YC-30 0.04 27.7 0.44-0.02

The 214(invention) 7-1 YC-30 0.06 28.1 0.44-0.02

The 215(invention) 8-1 YC-30-0.01 28.7 0.44-0.02

216(is relatively) 1-1 YC-30-0.04 30.1 0.42-0.05

The 217(invention) 6-1 YC-31 0.03 27.6 0.44-0.02

The 218(invention) 7-1 YC-31 0.06 28.1 0.44-0.02

The 219(invention) 8-1 YC-31-0.01 28.6 0.44-0.02

220(is relatively) 1-1 YC-31-0.06 30.0 0.42-0.05

From table 2-2, find out that clearly compare with the comparative sample that uses the emulsion exceed the scope of the invention, sample of the present invention shows higher photographic sensitivity and graininess and sharpness preferably.And reference sample and do not use other reference sample of yellow cyan colour coupler relatively to show higher light sensitivity and color rendition preferably.Sample of the present invention and all other reference samples relatively show higher photographic sensitivity and color rendition preferably, graininess and sharpness.In addition, with the sample with the emulsion 6-1 of high hexagonal plain film content and 7-1 preparation more have aspect photographic sensitivity and the graininess superior.

Through describing the present invention in detail and with reference to its special enforcement.Clearly, can carry out various changes and modifications under the situation of spirit and scope of the invention to those skilled in the art.

Claims (17)

1, a kind of silver halide color photographic light-sensitive material, comprise and wherein contain the support of one deck hydrophilic colloid layer at least, at least one deck photosensitive silver halide emulsion layer, wherein at least 50% formation at least the total projection area of the silver halide particle of one deck silver halide emulsion layer constitute by having the plain film shape particle that mean aspect ratio was at least 2: 1, and be included in yellow cyan coupler in one deck hydrophilic colloid layer at least.

2, a kind of silver halide color photographic light-sensitive material as claimed in claim 1; wherein yellow cyan become agent representative can with the coupling of oxidation state uncle arylamine developer solution; discharge and contain water-soluble 6-hydroxyl-2-pyridone-5-base azo group; water-soluble pyrazolone-4-base azo group; water-soluble 2-acyl amino phenylazo group, the cyan coupler of the residual compounds of water-soluble 5-amino-pyrazol-4-base azo group or water-soluble 2-sulfonamido phenylazo group.

3, a kind of silver halide color photographic light-sensitive material as claimed in claim 2, wherein said yellow cyan coupler be by formula (C I), and (C II), (C III) or (C IV) expression:

Wherein, Cp represents the cyan coupler residue; T represents timing group; K represents 0 or 1 integer; X representative by with X in contained N, O or S and (T) _KBonding and the divalent linker that links to each other with Q; Q represents arlydene or divalent heterocycle; R ₁And R ₂Independently represent hydrogen atom, carboxyl, sulfo group, cyano group, alkyl, naphthenic base, aryl, heterocyclic radical, carbamyl, sulfamoyl, carboxamide groups, sulfonamido or alkyl sulphonyl separately; R ₃Represent hydrogen atom, alkyl, naphthenic base, aryl or heterocyclic radical, its condition is T, X, Q, R ₁, R ₂And R ₃In at least one contains water soluble group, this group is selected from hydroxyl, carboxyl, sulfo group, amino, ammonium (ammoniumyl group) phosphono, phosphino-and hydroxyl sulfonyloxy; R ₄Represent acyl group or sulfonyl; R ₅Represent commutable group; J represents 0 to 4 integer, when j represents 2 or when bigger, R ₄Can be identical or different, its condition is T, X, Q, R ₄And R ₅In at least one is selected from hydroxyl, carboxyl, sulfo group, amino, ammonium, phosphono, the water soluble group of phosphino-and hydroxyl sulfonyloxy; R ₉Represent hydrogen atom, carboxyl, sulfo group, cyano group, alkyl, naphthenic base, aryl, alkoxy, alkoxy, cycloalkyloxy, aryloxy group, heterocyclic radical, carbamyl, sulfamoyl, carboxamide groups, sulfonamido or alkyl sulphonyl; And R ₁₀Represent hydrogen atom, alkyl, naphthenic base, aryl or heterocyclic radical, its condition is T, X, Q, R ₉And R ₁₀In at least one contains and is selected from hydroxyl, carboxyl, sulfo group, amino, ammonium, phosphono, the water soluble group of phosphino-and hydroxyl sulfonyloxy.

4, a kind of silver halide color photographic light-sensitive material as claimed in claim 1 also comprises the compound that formula (A) is represented:

Q-SM ¹（A）

Wherein, Q represents heterocyclic radical, and this group is by being selected from-SO as the divalent group of alkylidene and at least one ₃M ²,-COOM ²,-OH and-NR ¹R ²The direct or indirect bonding of group; M ¹And M ²Independently separately represent hydrogen atom, alkaline metal, quaternary ammonium or season phosphine; And R ¹And R ²Independent separately hydrogen atom or replacement or the substituted alkyl not represented.

5, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein constituting at least, the variation factor of the silver halide particle size of one deck silver halide emulsion layer is no more than 0.25.

6, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein the total projection area of the silver halide particle of one deck silver halide agent is by having two parallel planes as outside surface at least at least 50% formation, and the ratio of the length of the length of minor face and longest edge is no more than 2 hexahedron plain film shape silver halide particle and constitutes.

7, a kind of silver halide color photographic light-sensitive material as claimed in claim 1; the wherein said silver halide emulsion layer of one deck at least also comprises and at least aly has length breadth ratio and be at least 2; but average particle is long-pending or other different plain film shape emulsion of silver halide component, and the perhaps described silver halide emulsion layer of one deck at least also comprises silver halide particle except that platy shaped particle in same photographic layer.

8, a kind of silver halide color photographic light-sensitive material as claimed in claim 5; the wherein said silver emulsion of one deck at least also comprises and at least aly has length breadth ratio and be at least 2; but average particle is long-pending or other different plain film shape emulsion of silver halide component, and the perhaps described silver halide emulsion layer of one deck at least also comprises other silver halide particle except that platy shaped particle in same photographic layer.

9, a kind of silver halide color photographic light-sensitive material as claimed in claim 6; the wherein said silver halide emulsion layer of one deck at least also comprises and at least aly has length breadth ratio and be at least 2; but the hexahedron plain film shape emulsion in the grain pattern; long-pending or other the different plain film shape emulsion of silver halide component of average particle; the perhaps described silver halide emulsion layer of one deck at least also comprises other silver halide particle except that platy shaped particle.

10, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein said yellow cyan coupler is represented by formula (C I):

Wherein, Cp represents the cyan coupler residue; T represents timing group; K represents 0 or 1 integer; X representative is by being contained in the N among the X, O or S and (T) _KBonding and the bivalence linking base group that is connected with Q; Q represents arlydene or divalent heterocycle; R ₁And R ₂Independently represent hydrogen atom, carboxyl, sulfo group, cyano group, alkyl, naphthenic base, aryl, heterocyclic radical, carbamyl, sulfamoyl, carboxamide groups, sulfonamido or alkyl sulphonyl separately; And R ₃Represent hydrogen atom, alkyl, naphthenic base, aryl or heterocyclic radical, its condition is T, X, Q, R ₁, R ₂And R ₃In at least one contains and is selected from hydroxyl, carboxyl, sulfo group, amino, ammonium, phosphono, the water soluble group of phosphino-and hydroxyl sulfonyloxy.

11, a kind of silver halide color photographic light-sensitive material as claimed in claim 10, wherein ,-(T) _K-X-Q-representative

12, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein, described yellow cyan coupler content in photosensitive material is 0.005 to 0.30g/m ²

13, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein, in the visible-range of yellow cyan coupler between 400nm and 500nm a peak absorbance is arranged, this Huang cyan coupler forms the cyan dye that a peak absorbance is arranged in the visible-range that has between 630nm and 750nm, and with uncle's arylamine developer solution coupling of oxidation state.

14, a kind of silver halide color photographic light-sensitive material as claimed in claim 1 comprises the red sensing coppering silver emulsion that contains described yellow cyan coupler.

15, a kind of silver halide color photographic light-sensitive material as claimed in claim 1, wherein, at least 85% the formation total projection area of the silver halide particle of one deck silver halide emulsion layer at least constitutes by having the plain film shape particle that length breadth ratio was at least 2: 1.

16, a kind of silver halide color photographic light-sensitive material as claimed in claim 6, wherein at least 90% formation at least the total projection area of the silver halide particle of one deck silver halide emulsion layer constitute by described hexahedron plain film shape silver halide particle.

17, a kind of silver halide color photographic light-sensitive material as claimed in claim 4, wherein said formula (A) compound content in photosensitive material is 1 * 10 ^-7To 1 * 10 ^-3Mol/m ²